Highly-fluorescent and photo-stable chromophores for wavelength conversion

ABSTRACT

The invention provides highly fluorescent materials comprising a heterocyclic systems represented by formula (I): D 1 -Het L-Het   i D 2 , wherein i is  0  and Het is 
                         
wherein X is —S—. The chromophores are particularly useful for absorption and emission of photons in the visible and near infrared wavelength range. The photo-stable highly luminescent chromophores are useful in various applications, including in wavelength conversion films. Wavelength conversion films have the potential to significantly enhance the solar harvesting efficiency of photovoltaic or solar cell devices.

CROSS-REFERENCE TO RELATED APPLICATIONS

Any and all applications for which a foreign or domestic priority claimis identified in the Application Data Sheet as filed with the presentapplication are hereby incorporated by reference under 37 CFR 1.57.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention generally relates to photo-stable highlyluminescent chromophores which are useful in various applications,including in wavelength conversion films. Wavelength conversion filmshave the potential to significantly enhance the solar harvestingefficiency of photovoltaic or solar cell devices. In particular, thechromophores described herein are useful for wavelength conversion ofvisible and near infrared radiation.

Description of the Related Art

In recent years, with the need for new optical light collection systems,fluorescence-based solar collectors, fluorescence-activated displays,and single-molecule spectroscopy, various approaches for preparingluminescent chromophores have been explored. However, many technicalissues have yet to be overcome.

In the form of monomers, oligomers or polymers,2H-benzo[d][1,2,3]triazole derivatives have recently become of highinterest due to their usefulness in designing electrochromic andoptoelectronic devices. Typical derivatives of2H-benzo[d][1,2,3]triazole from the literature are composed ofelectron-donating substituents at the N-2, C-4 and C-7 positions, asshown below in Structure A, where typical electron-donors described inthe literature comprise alkyl 1-hydroxyphenyl and 1-alkoxyphenyl groups,and typical electron donor groups at N-2 described in the literaturecomprise alkyl, 2-hydroxyphenyl, and 2-alkoxyphenyl. These derivativesexhibit strong absorption and fluorescence bands in UV and/or shortvisible wavelength region.

Chromophores based on 2-alkylbenzotriazole scaffold have also become ofsignificant interest in recent years. The majority of these types ofcompounds comprise 2-alkyl-4,7-dithienylbenzotriazole units, similar toStructure B, shown below, with various substituents, usually in the formof polymers and copolymers.

Chromophores based on benzothiadiazole, shown by Structure C, are themost common, especially with thienyl groups as electron donors, whichare convenient building blocks for fluorescent polymers.

While much of the work on organic luminescent dyes has focused on thetwo ring core structure described above, there has been very little workreported on luminescent dyes with three ring cores. Some initial studiesof compounds with the following three ring core structures have beenreported:

where X is N, S, or Se, and D₁ and D₂ are hydrogen, furan, or thiophen,and are described in the following publications: Japanese patentapplications JP19810054380 and JP19810107409, Organic Letters 2011,13(17), 4612, Journal of Materials Chemistry 2012, 22, 4687, OrganicLetters 2011, 13(9), 2338, Spectrochimica Acta Part A 2007, 66, 849,Spectrochimica Part A 2004, 60, 2005, Journal of Chemical Informationand Modeling 2011, 51, 2904, Chem. Commun. 2012, 48, 1236, OrganicLetters 2012, 14(2), 532, Journal of Organic Chemistry 1986, 51, 979,Tetrahedron Letters 1984, 25(20), 2073, Polymer 2012, 53, 1465, Journalof the American Chemical Society 2012, 134, 2599.

One of the useful properties of fluorescence (or photo-luminescent) dyesis that they have the ability to absorb light photons of a particularwavelength, and re-emit the photons at a different wavelength. Thisphenomenon also makes them useful in the photovoltaic industry. Theutilization of solar energy offers a promising alternative energy sourceto the traditional fossil fuels, and therefore, the development ofdevices that can convert solar energy into electricity, such asphotovoltaic devices (also known as solar cells), has drawn significantattention in recent years. Several different types of maturephotovoltaic devices have been developed, including a Silicon baseddevice, a III-V and II-VI PN junction device, aCopper-Indium-Gallium-Selenium (CIGS) thin film device, an organicsensitizer device, an organic thin film device, and a CadmiumSulfide/Cadmium Telluride (CdS/CdTe) thin film device, to name a few.However, the photoelectric conversion efficiency of many of thesedevices still has room for improvement and development of techniques toimprove this efficiency has been an ongoing challenge for manyresearchers.

One technique developed to improve the efficiency of photovoltaicdevices is to utilize a wavelength conversion film. Many of thephotovoltaic devices are unable to effectively utilize the entirespectrum of light as the materials on the device absorb certainwavelengths of light (typically the shorter UV wavelengths) instead ofallowing the light to pass through to the photoconductive material layerwhere it is converted into electricity. Application of a wavelengthconversion film absorbs the shorter wavelength photons and re-emits themat more favorable longer wavelengths, which can then be absorbed by thephotoconductive layer in the device, and converted into electricity.

While there have been numerous disclosures of wavelength conversioninorganic mediums used in photovoltaic devices and solar cells, therehas been very little work reported on the use of photo-luminescentorganic mediums for efficiency improvements in photovoltaic devices. Theuse of luminescent down-shifting materials to improve the efficiency ofphotovoltaic devices and solar cells has been disclosed in severalpublications, including U.S. Pat. No. 7,791,157, and U.S. PatentApplication Publication Nos. 2009/0151785, 2010/0294339, and2010/0012183. All of these publications include example embodiments ofluminescent down-shifting mediums applied to a photovoltaic device orsolar cell in which the medium is composed of an inorganic material. Theuse of an organic medium, as opposed to an inorganic medium, isattractive in that organic materials are typically cheaper and easier touse, making them a better economical choice. However, most of thecurrently available organic luminescent dyes are typically notphoto-stable for long periods of time, and therefore unusable inphotovoltaic applications which require consistent performance for 20+years.

SUMMARY OF THE INVENTION

Novel compounds of heterocyclic system are disclosed. These compoundsare useful as chromophores that provide desirable optical properties andgood photo-stability.

Some embodiments provide a chromophore represented by formula I:D₁-Het

L-Het

_(i)D₂  (I)wherein Het is selected from the group consisting of:

wherein i is 0 or an integer in the range of 1 to 100, X is selectedfrom the group consisting of —N(A₀)-, —O—, —S—, —Se—, and —Te—; and Z isselected from the group consisting of —N(R_(a))—, —O—, —S—, —Se—, and—Te—.

Each A₀ of formula I is selected from the group consisting of hydrogen,optionally substituted alkyl, optionally substituted alkenyl, optionallysubstituted heteroalkyl, optionally substituted aryl, optionallysubstituted heteroaryl, optionally substituted amino, optionallysubstituted amido, optionally substituted cyclic amido, optionallysubstituted cyclic imido, optionally substituted alkoxy, optionallysubstituted acyl, optionally substituted carboxy, and optionallysubstituted carbonyl.

Each R_(a), R_(b), and R_(c), of formula I are independently selectedfrom the group consisting of hydrogen, optionally substituted alkyl,optionally substituted alkoxyalkyl, optionally substituted alkenyl,optionally substituted heteroalkyl, optionally substitutedheteroalkenyl, optionally substituted aryl, optionally substitutedarylalkyl, optionally substituted heteroaryl, optionally substitutedcylcoalkyl, optionally substituted cycloalkenyl, optionally substitutedcycloheteroalkyl, optionally substituted cycloheteroalkenyl, optionallysubstituted amino, optionally substituted amido, optionally substitutedcyclic amido, optionally substituted cyclic imido, optionallysubstituted alkoxy, optionally substituted carboxy, and optionallysubstituted carbonyl; or R_(a) and R_(b), or R_(b) and R_(c), or R_(a)and R_(c), together form an optionally substituted ring or an optionallysubstituted polycyclic ring system, wherein each ring is independentlycycloalkyl, aryl, heterocyclyl, or heteroaryl.

Each D₁ and D₂ of formula I are independently selected from the groupconsisting of hydrogen, optionally substituted alkoxy, optionallysubstituted aryloxy, optionally substituted acyloxy, optionallysubstituted alkyl, optionally substituted aryl, optionally substitutedheteroaryl, optionally substituted amino, amido, cyclic amido, cyclicimido, -aryl-NR′R″, -ary-aryl-NR′R″, and -heteroaryl-heteroaryl-R′;wherein R′ and R″ are independently selected from the group consistingof optionally substituted alkyl, optionally substituted alkenyl, andoptionally substituted aryl; or one or both of R′ and R″ forms a fusedheterocyclic ring with aryl to which the N is attached to; provided thatD₁ and D₂ are not both hydrogen, and D₁ and D₂ are not optionallysubstituted thiophene or optionally substituted furan.

L of formula I is independently selected from the group consisting ofoptionally substituted alkyl, optionally substituted aryl, optionallysubstituted heteroaryl, amino, amido, imido, optionally substitutedalkoxy, acyl, carboxy, provided that L is not optionally substitutedthiophene or optionally substituted furan.

Some embodiments of the invention provide a chromophore represented byformula IIa or formula IIb:

wherein Het₂ is selected from the group consisting of:

wherein Z is selected from the group consisting of —N(R_(a))—, —O—, —S—,—Se—, and —Te—.

Each of the R_(a), R_(b), and R_(c), in formula IIa and formula IIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkyl, optionally substituted alkoxyalkyl, optionallysubstituted alkenyl, optionally substituted heteroalkyl, optionallysubstituted heteroalkenyl, optionally substituted aryl, optionallysubstituted arylalkyl, optionally substituted heteroaryl, optionallysubstituted cylcoalkyl, optionally substituted cycloalkenyl, optionallysubstituted cycloheteroalkyl, optionally substituted cycloheteroalkenyl,optionally substituted amino, optionally substituted amido, optionallysubstituted cyclic amido, optionally substituted cyclic imido,optionally substituted alkoxy, optionally substituted carboxy, andoptionally substituted carbonyl; or R_(a) and R_(b), or R_(b) and R_(c),or R_(a) and R_(c), together form an optionally substituted ring or anoptionally substituted polycyclic ring system, wherein each ring isindependently cycloalkyl, aryl, heterocyclyl, or heteroaryl.

Each of the R_(d) and R_(e) in formula IIa and formula IIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkyl, optionally substituted alkoxyalkyl, optionallysubstituted alkenyl, optionally substituted heteroalkyl, optionallysubstituted heteroalkenyl, optionally substituted aryl, optionallysubstituted arylalkyl, optionally substituted heteroaryl, optionallysubstituted cylcoalkyl, optionally substituted cycloalkenyl, optionallysubstituted cycloheteroalkyl, optionally substituted cycloheteroalkenyl,optionally substituted amino, optionally substituted amido, optionallysubstituted cyclic amido, optionally substituted cyclic imido,optionally substituted alkoxy, optionally substituted carboxy, andoptionally substituted carbonyl; or R_(d) and R_(e) together form anoptionally substituted ring or an optionally substituted polycyclic ringsystem, wherein each ring is independently cycloalkyl, aryl,heterocyclyl, or heteroaryl.

Each of D₁, D₂, D₃, and D₄ in formula IIa and formula IIb is eachindependently selected from the group consisting of hydrogen, optionallysubstituted alkoxy, optionally substituted aryloxy, optionallysubstituted acyloxy, optionally substituted alkyl, optionallysubstituted aryl, optionally substituted heteroaryl, optionallysubstituted amino, amido, cyclic amido, cyclic imido, -aryl-NR′R″,-ary-aryl-NR′R″, and -heteroaryl-heteroaryl-R′; wherein R′ and R″ areindependently selected from the group consisting of optionallysubstituted alkyl, optionally substituted alkenyl, and optionallysubstituted aryl; or one or both of R′ and R″ forms a fused heterocyclicring with aryl to which the N is attached to; provided that D₁ and D₂are not both hydrogen, and D₁ and D₂ are not optionally substitutedthiophene or optionally substituted furan.

Some embodiments provide a chromophore represented by formula IIIa andformula IIIb:

wherein Het₃ is selected from the group consisting of:

and wherein X is selected from the group consisting of —N(A₀)-, —O—,—S—, —Se—, and —Te—.

Each A₀ of formula IIIa and formula IIIb is selected from the groupconsisting of hydrogen, optionally substituted alkyl, optionallysubstituted alkenyl, optionally substituted heteroalkyl, optionallysubstituted aryl, optionally substituted heteroaryl, optionallysubstituted amino, optionally substituted amido, optionally substitutedcyclic amido, optionally substituted cyclic imido, optionallysubstituted alkoxy, optionally substituted acyl, optionally substitutedcarboxy, and optionally substituted carbonyl.

Each R_(a), R_(b), and R_(c), of formula IIIa and formula IIIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkyl, optionally substituted alkoxyalkyl, optionallysubstituted alkenyl, optionally substituted heteroalkyl, optionallysubstituted heteroalkenyl, optionally substituted aryl, optionallysubstituted arylalkyl, optionally substituted heteroaryl, optionallysubstituted cylcoalkyl, optionally substituted cycloalkenyl, optionallysubstituted cycloheteroalkyl, optionally substituted cycloheteroalkenyl,optionally substituted amino, optionally substituted amido, optionallysubstituted cyclic amido, optionally substituted cyclic imido,optionally substituted alkoxy, optionally substituted carboxy, andoptionally substituted carbonyl; or R_(a) and R_(b), or R_(b) and R_(c),or R_(a) and R_(c), together form an optionally substituted ring or anoptionally substituted polycyclic ring system, wherein each ring isindependently cycloalkyl, aryl, heterocyclyl, or heteroaryl.

Each R_(d) and R_(e) of formula IIIa and formula IIIb is independentlyselected from the group consisting of hydrogen, optionally substitutedalkyl, optionally substituted alkoxyalkyl, optionally substitutedalkenyl, optionally substituted heteroalkyl, optionally substitutedheteroalkenyl, optionally substituted aryl, optionally substitutedarylalkyl, optionally substituted heteroaryl, optionally substitutedcylcoalkyl, optionally substituted cycloalkenyl, optionally substitutedcycloheteroalkyl, optionally substituted cycloheteroalkenyl, optionallysubstituted amino, optionally substituted amido, optionally substitutedcyclic amido, optionally substituted cyclic imido, optionallysubstituted alkoxy, optionally substituted carboxy, and optionallysubstituted carbonyl; or R_(d) and R_(e) together form an optionallysubstituted ring or an optionally substituted polycyclic ring system,wherein each ring is independently cycloalkyl, aryl, heterocyclyl, orheteroaryl.

Each D₁, D₂, D₃, and D₄ of formula IIIa and formula IIIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkoxy, optionally substituted aryloxy, optionallysubstituted acyloxy, optionally substituted alkyl, optionallysubstituted aryl, optionally substituted heteroaryl, optionallysubstituted amino, amido, cyclic amido, cyclic imido, -aryl-NR′R″,-ary-aryl-NR′R″, and -heteroaryl-heteroaryl-R′; wherein R′ and R″ areindependently selected from the group consisting of optionallysubstituted alkyl, optionally substituted alkenyl, and optionallysubstituted aryl; or one or both of R′ and R″ forms a fused heterocyclicring with aryl to which the N is attached to; provided that D₁ and D₂are not both hydrogen, and D₁ and D₂ are not optionally substitutedthiophene or optionally substituted furan.

Some embodiments also provide a wavelength conversion luminescent mediumcomprising an optically transparent polymer matrix and at least oneluminescent dye comprising a chromophore as disclosed herein.

Some embodiments also provide a photovoltaic module comprising at leastone photovoltaic device or solar cell, and a wavelength conversionluminescent medium as disclosed herein, wherein the wavelengthconversion luminescent medium is positioned such that the incident lightpasses through the wavelength conversion luminescent medium prior toreaching the photovoltaic device or solar cell.

Some embodiments provide a method for improving the performance of aphotovoltaic device or solar cell, comprising applying a wavelengthconversion luminescent medium as disclosed herein directly onto thelight incident side of the photovoltaic device or solar cell, orencapsulate the wavelength conversion luminescent medium in thephotovoltaic device or solar cell.

Further aspects, features and advantages of this invention will becomeapparent from the detailed description of the preferred embodimentswhich follow.

DETAILED DESCRIPTION

One of the useful properties of fluorescence (or photo-luminescent) dyesis that they have the ability to absorb light photons of a particularwavelength, and re-emit the photons at a different wavelength. Thisphenomenon also makes them useful in the photovoltaic industry.

The chromophores represented by general formula I, formula IIa, formulaIIb, formula IIIa, and formula IIIb, are useful as fluorescent dyes invarious applications, including in wavelength conversion films. As shownin the formulae, the dye comprises a benzo heterocyclic system.Additional detail and examples, without limiting the scope of theinvention, on the types of compounds that can be used are describedbelow.

The term “alkyl” refers to a branched or straight fully saturatedacyclic aliphatic hydrocarbon group (i.e. composed of carbon andhydrogen containing no double or triple bonds). Alkyls include, but arenot limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tertiary butyl, pentyl, hexyl, and the like.

The term “heteroalkyl” used herein refers to an alkyl group comprisingone or more heteroatoms. When two or more heteroatoms are present, theymay be the same or different.

The term “cycloalkyl” used herein refers to saturated aliphatic ringsystem radical having three to twenty carbon atoms including, but notlimited to, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and thelike.

The term “alkenyl” used herein refers to a monovalent straight orbranched chain radical of from two to twenty carbon atoms containing atleast one carbon double bond including, but not limited to, 1-propenyl,2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, and the like.

The term “alkynyl” used herein refers to a monovalent straight orbranched chain radical of from two to twenty carbon atoms containing acarbon triple bond including, but not limited to, 1-propynyl, 1-butynyl,2-butynyl, and the like.

The term “aryl” used herein refers to homocyclic aromatic radicalwhether one ring or multiple fused rings. Examples of aryl groupsinclude, but are not limited to, phenyl, naphthyl, phenanthrenyl,naphthacenyl, fluorenyl, pyrenyl, and the like. Further examplesinclude:

The term “alkaryl” or “alkylaryl” used herein refers to analkyl-substituted aryl radical. Examples of alkaryl include, but are notlimited to, ethylphenyl, 9,9-dihexyl-9H-fluorene, and the like.

The term “aralkyl” or “arylalkyl” used herein refers to anaryl-substituted alkyl radical. Examples of aralkyl include, but are notlimited to, phenylpropyl, phenylethyl, and the like.

The term “heteroaryl” used herein refers to an aromatic group comprisingone or more heteroatoms, whether one ring or multiple fused rings. Whentwo or more heteroatoms are present, they may be the same or different.In fused ring systems, the one or more heteroatoms may be present inonly one of the rings. Examples of heteroaryl groups include, but arenot limited to, benzothiazyl, benzoxazyl, quinazolinyl, quinolinyl,isoquinolinyl, quinoxalinyl, pyridinyl, pyrrolyl, oxazolyl, indolyl,thiazyl and the like. Further examples of substituted and unsubstitutedheteroaryl rings include:

The term “alkoxy” used herein refers to straight or branched chain alkylradical covalently bonded to the parent molecule through an —O— linkage.Examples of alkoxy groups include, but are not limited to, methoxy,ethoxy, propoxy, isopropoxy, butoxy, n-butoxy, sec-butoxy, t-butoxy andthe like.

The term “heteroatom” used herein refers to any atom that is not C(carbon) or H (hydrogen). Examples of heteroatoms include S (sulfur), N(nitrogen), and O (oxygen).

The term “cyclic amino” used herein refers to either secondary ortertiary amines in a cyclic moiety. Examples of cyclic amino groupsinclude, but are not limited to, aziridinyl, piperidinyl,N-methylpiperidinyl, and the like.

The term “cyclic imido” used herein refers to an imide in the radical ofwhich the two carbonyl carbons are connected by a carbon chain. Examplesof cyclic imide groups include, but are not limited to,1,8-naphthalimide, pyrrolidine-2,5-dione, 1H-pyrrole-2,5-dione, and thelikes.

The term “acyl” used herein refers to a radical —C(═O)R.

The term “aryloxy” used herein refers to an aryl radical covalentlybonded to the parent molecule through an —O— linkage.

The term “acyloxy” used herein refers to a radical —O—C(═O)R.

The term “carbamoyl” used herein refers to a radical —C(═O)NH₂.

The term “carbonyl” used herein refers to a functional group C═O.

The term “carboxy” used herein refers to a radical —COOR.

The term “ester” used herein refers to a functional group RC(═O)OR′.

The term “amido” used herein refers to a radical —C(═O)NR′R″.

The term “amino” used herein refers to a radical —NR′R″.

The term “heteroamino” used herein refers to a radical —NR′R″ wherein R′and/or R″ comprises a heteroatom.

The term “heterocyclic amino” used herein refers to either secondary ortertiary amines in a cyclic moiety wherein the group further comprises aheteroatom.

The term “cycloamido” used herein refers to an amido radical of—C(═O)NR′R″ wherein R′ and R″ are connected by a carbon chain.

As used herein, a substituted group is derived from the unsubstitutedparent structure in which there has been an exchange of one or morehydrogen atoms for another atom or group. When substituted, thesubstituent group(s) is (are) one or more group(s) individually andindependently selected from C₁-C₆ alkyl, C₁-C₆ alkenyl, C₁-C₆ alkynyl,C₃-C₇ cycloalkyl (optionally substituted with a moiety selected from thegroup consisting of halo, alkyl, alkoxy, carboxyl, haloalkyl, CN,—SO₂-alkyl, —CF₃, and —OCF₃), cycloalkyl geminally attached, C₁-C₆heteroalkyl, C₃-C₁₀ heterocycloalkyl (e.g., tetrahydrofuryl) (optionallysubstituted with a moiety selected from the group consisting of halo,alkyl, alkoxy, carboxyl, CN, —SO₂-alkyl, —CF₃, and —OCF₃), aryl(optionally substituted with a moiety selected from the group consistingof halo, alkyl, arylalkyl, alkoxy, aryloxy, carboxyl, amino, imido,amido (carbamoyl), optionally substituted cyclic imido, cylic amido, CN,—NH—C(═O)-alkyl, —CF₃, —OCF₃, and aryl optionally substituted with C₁-C₆alkyl), arylalkyl (optionally substituted with a moiety selected fromthe group consisting of halo, alkyl, alkoxy, aryl, carboxyl, CN,—SO₂-alkyl, —CF₃, and —OCF₃), heteroaryl (optionally substituted with amoiety selected from the group consisting of halo, alkyl, alkoxy, aryl,heteroaryl, aralkyl, carboxyl, CN, —SO₂-alkyl, —CF₃, and —OCF₃), halo(e.g., chloro, bromo, iodo and fluoro), cyano, hydroxy, optionallysubstituted cyclic imido, amino, imido, amido, —CF₃, C₁-C₆ alkoxy(optionally substituted with halo, alkyl, alkoxy, aryl, carboxyl, CN,—SO₂-alkyl, —CF₃, and —OCF₃), aryloxy, acyloxy, sulfhydryl (mercapto),halo(C₁-C₆)alkyl, C₁-C₆ alkylthio, arylthio, mono- and di-(C₁-C₆)alkylamino, quaternary ammonium salts, amino(C₁-C₆)alkoxy,hydroxy(C₁-C₆)alkylamino, amino(C₁-C₆)alkylthio, cyanoamino, nitro,carbamoyl, keto (oxy), carbonyl, carboxy, acyl, glycolyl, glycyl,hydrazino, guanyl, sulfamyl, sulfonyl, sulfinyl, thiocarbonyl,thiocarboxy, sulfonamide, ester, C-amide, N-amide, N-carbamate,O-carbamate, urea and combinations thereof. Wherever a substituent isdescribed as “optionally substituted” that substituent can besubstituted with the above substituents.

Formula I

Some embodiments provide a chromophore having one of the structuresbelow:

wherein Het is selected from the group consisting of:

wherein i is 0 or an integer in the range of 1 to 100, X is selectedfrom the group consisting of —N(A₀)-, —O—, —S—, —Se—, and —Te—, and Z isselected from the group consisting of —N(R_(a))—, —O—, —S—, —Se—, and—Te—.

Each A₀ in formula I is selected from the group consisting of hydrogen,optionally substituted alkyl, optionally substituted alkenyl, optionallysubstituted heteroalkyl, optionally substituted aryl, optionallysubstituted heteroaryl, optionally substituted amino, optionallysubstituted amido, optionally substituted cyclic amido, optionallysubstituted cyclic imido, optionally substituted alkoxy, optionallysubstituted acyl, optionally substituted carboxy, and optionallysubstituted carbonyl. In some embodiments, each A₀ of formula I isselected from the group consisting of hydrogen, optionally substitutedC₁₋₈ alkyl, optionally substituted C₂₋₈ alkenyl, and optionallysubstituted C₆₋₁₀ aryl.

Each R_(a), R_(b), and R_(c), of formula I independently selected fromthe group consisting of hydrogen, optionally substituted alkyl,optionally substituted alkoxyalkyl, optionally substituted alkenyl,optionally substituted heteroalkyl, optionally substitutedheteroalkenyl, optionally substituted aryl, optionally substitutedarylalkyl, optionally substituted heteroaryl, optionally substitutedcylcoalkyl, optionally substituted cycloalkenyl, optionally substitutedcycloheteroalkyl, optionally substituted cycloheteroalkenyl, optionallysubstituted amino, optionally substituted amido, optionally substitutedcyclic amido, optionally substituted cyclic imido, optionallysubstituted alkoxy, optionally substituted carboxy, and optionallysubstituted carbonyl; or R_(a) and R_(b), or R_(b) and R_(c), or R_(a)and R_(c), together form an optionally substituted ring or an optionallysubstituted polycyclic ring system, wherein each ring is independentlycycloalkyl, aryl, heterocyclyl, or heteroaryl.

In some embodiments, each R_(a), R_(b), and R_(c), of formula I areindependently selected from the group consisting of hydrogen, optionallysubstituted C₁₋₈ alkyl, optionally substituted C₆₋₁₀ aryl, andoptionally substituted C₆₋₁₀ heteroaryl. In some embodiments, eachR_(a), R_(b), and R_(c), of formula I are independently selected fromthe group consisting of hydrogen, C₁₋₈ alkyl, C₆₋₁₀ aryl, and C₆₋₁₀heteroaryl, wherein C₁₋₈ alkyl, C₆₋₁₀ aryl, and C₆₋₁₀ heteroaryl mayeach be optionally substituted by optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₁₋₈ alkoxy, halo, cyano, carboxyl,optionally substituted C₆₋₁₀ aryl, optionally substituted C₆₋₁₀ aryloxy,

In some embodiments, R_(a) and R_(b), or R_(b) and R_(c), or R_(a) andR_(c), together form an optionally substituted ring system selected fromthe group consisting of:

Each D₁ and D₂ of formula I are each independently selected from thegroup consisting of hydrogen, optionally substituted alkoxy, optionallysubstituted aryloxy, optionally substituted acyloxy, optionallysubstituted alkyl, optionally substituted aryl, optionally substitutedheteroaryl, optionally substituted amino, amido, cyclic amido, andcyclic imido, -aryl-NR′R″, -aryl-aryl-NR′R″, and-heteroaryl-heteroaryl-R′; wherein R′ and R″ are independently selectedfrom the group consisting of optionally substituted alkyl, optionallysubstituted alkenyl, and optionally substituted aryl; or one or both ofR′ and R″ forms a fused heterocyclic ring with aryl to which the N isattached to; provided that D₁ and D₂ are not both hydrogen, and D₁ andD₂ are not optionally substituted thiophene or optionally substitutedfuran.

In some embodiments, the chromophore is represented by formula I,wherein D₁ and D₂ are each independently selected from the groupconsisting of alkoxyaryl, -aryl-NR′R″, and -aryl-aryl-NR′R″; wherein R′and R″ are independently selected from the group consisting of alkyl andaryl optionally substituted by alkyl, alkoxy, or —C(═O)R; wherein R isoptionally substituted aryl or optionally substituted alkyl; or one orboth of R′ and R″ forms a fused heterocyclic ring with aryl to which theN is attached to.

In some embodiments, each D₁ and D₂ of formula I are independently C₆₋₁₀aryl or optionally substituted C₆₋₁₀ aryl. The substituent(s) on theC₆₋₁₀ aryl may be selected from the group consisting of —NR′R″, —C₆₋₁₀aryl-NR′R″, C₁₋₈ alkyl and C₁₋₈ alkoxy; wherein R′ and R″ areindependently selected from the group consisting of C₁₋₈ alkyl, C₁₋₈alkoxy, C₆₋₁₀ aryl, C₆₋₁₀ aryl-C₁₋₈ alkyl, C₆₋₁₀ aryl-C₁₋₈ alkoxy, andC₆₋₁₀ aryl-C(═O)R, wherein R is optionally substituted C₁₋₈ alkyl,optionally substituted C₁₋₈ alkoxy or optionally substituted C₆₋₁₀ aryl;or one or both of R′ and R″ forms a fused heterocyclic ring with aryl towhich the N is attached to.

L of formula I is independently selected from the group consisting ofoptionally substituted alkyl, optionally substituted aryl, optionallysubstituted heteroaryl, amino, amido, imido, optionally substitutedalkoxy, acyl, carboxy, provided that L is not optionally substitutedthiophene or optionally substituted furan.

In some embodiments, the chromophore is represented by formula I,wherein L is independently selected from the group consisting ofhaloalkyl, alkylaryl, alkyl substituted heteroaryl, arylalkyl,heteroamino, heterocyclic amino, cycloamido, cycloimido, aryloxy,acyloxy, alkylacyl, arylacyl, alkylcarboxy, arylcarboxy, optionallysubstituted phenyl, and optionally substituted naphthyl.

In some embodiments, the chromophore is represented by formula I,provided that when Het is:

R_(a) and R_(b) are not both hydrogen, and D₁ and D₂ are independentlyselected from the group consisting of:

In some embodiments, the chromophore is represented by formula I,provided that when Het is

R_(a) and R_(b) are not both hydrogen.

In some embodiments, the chromophore is represented by formula I,wherein Het is

X is selected from the group consisting of —N(A₀)- and —Se—, Z isselected from the group consisting of —N(R_(a))— and —S—, and D₁ and D₂are independently selected from the group consisting of:

In some embodiments, the chromophore is represented by formula I,wherein Het is:

and X is selected from the group consisting of —S— and —Se—, Z is —S—,and D₁ and D₂ are independently selected from the group consisting of:

In some embodiments, the chromophore is represented by formula I,wherein Het is

and wherein D₁ and D₂ are not hydroxy, or

and D₁ and D₂ do not comprise bromine.

In formulae I, i is 0 or an integer in the range of 1 to 100. In someembodiments, i is 0 or an integer in the range of 1 to 50, 1 to 30, 1 to10, 1 to 5, or 1 to 3. In some embodiments, i is 0, 1, 2, 3, 4, 5, 6, 7,8, 9, or 10.

Formula II

Some embodiments of the invention provide a chromophore represented byformula IIa or formula IIb:

wherein Het₂ is selected from the group consisting of:

wherein Z is selected from the group consisting of —N(R_(a))—, —O—, —S—,—Se—, and —Te—.

Each of the R_(a), R_(b), and R_(c), in formula IIa and formula IIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkyl, optionally substituted alkoxyalkyl, optionallysubstituted alkenyl, optionally substituted heteroalkyl, optionallysubstituted heteroalkenyl, optionally substituted aryl, optionallysubstituted arylalkyl, optionally substituted heteroaryl, optionallysubstituted cylcoalkyl, optionally substituted cycloalkenyl, optionallysubstituted cycloheteroalkyl, optionally substituted cycloheteroalkenyl,optionally substituted amino, optionally substituted amido, optionallysubstituted cyclic amido, optionally substituted cyclic imido,optionally substituted alkoxy, optionally substituted carboxy, andoptionally substituted carbonyl; or R_(a) and R_(b), or R_(b) and R_(c),or R_(a) and R_(c), together form an optionally substituted ring or anoptionally substituted polycyclic ring system, wherein each ring isindependently cycloalkyl, aryl, heterocyclyl, or heteroaryl.

Each of the R_(d) and R_(e) in formula IIa and formula IIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkyl, optionally substituted alkoxyalkyl, optionallysubstituted alkenyl, optionally substituted heteroalkyl, optionallysubstituted heteroalkenyl, optionally substituted aryl, optionallysubstituted arylalkyl, optionally substituted heteroaryl, optionallysubstituted cylcoalkyl, optionally substituted cycloalkenyl, optionallysubstituted cycloheteroalkyl, optionally substituted cycloheteroalkenyl,optionally substituted amino, optionally substituted amido, optionallysubstituted cyclic amido, optionally substituted cyclic imido,optionally substituted alkoxy, optionally substituted carboxy, andoptionally substituted carbonyl; or R_(d) and R_(e) together form anoptionally substituted ring or an optionally substituted polycyclic ringsystem, wherein each ring is independently cycloalkyl, aryl,heterocyclyl, or heteroaryl.

In some embodiments, each R_(a), R_(b), and R_(c) is independentlyselected from the group consisting of hydrogen, optionally substitutedC₁₋₈ alkyl, optionally substituted C₆₋₁₀ aryl, and optionallysubstituted C₆₋₁₀ heteroaryl. In some embodiments, each R_(a), R_(b),and R_(c), of formula I are independently selected from the groupconsisting of hydrogen, C₁₋₈ alkyl, C₆₋₁₀ aryl, and C₆₋₁₀ heteroaryl,wherein C₁₋₈ alkyl, C₆₋₁₀ aryl, and C₆₋₁₀ heteroaryl may each beoptionally substituted by optionally substituted C₃₋₁₀ cycloalkyl,optionally substituted C₁₋₈ alkoxy, halo, cyano, carboxyl, optionallysubstituted C₆₋₁₀ aryl, optionally substituted C₆₋₁₀ aryloxy,

In some embodiments, R_(a) and R_(b), or R_(b) and R_(c), or R_(a) andR_(c), together form an optionally substituted ring system selected fromthe group consisting of:

Each of D₁, D₂, D₃, and D₄ in formula IIa and formula IIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkoxy, optionally substituted aryloxy, optionallysubstituted acyloxy, optionally substituted alkyl, optionallysubstituted aryl, optionally substituted heteroaryl, optionallysubstituted amino, amido, cyclic amido, and cyclic imido, -aryl-NR′R″,-aryl-aryl-NR′R″, and -heteroaryl-heteroaryl-R′; wherein R′ and R″ areindependently selected from the group consisting of optionallysubstituted alkyl, optionally substituted alkenyl, and optionallysubstituted aryl; or one or both of R′ and R″ forms a fused heterocyclicring with aryl to which the N is attached to; provided that D₁ and D₂are not both hydrogen, and D₁ and D₂ are not optionally substitutedthiophene or optionally substituted furan.

In some embodiments, the chromophore is represented by formula IIa orIIb, wherein D₁ and D₂ are each independently selected from the groupconsisting of alkoxyaryl, -aryl-NR′R″, and -aryl-aryl-NR′R″; wherein R′and R″ are independently selected from the group consisting of alkyl andaryl optionally substituted by alkyl, alkoxy, or —C(═O)R; wherein R isoptionally substituted aryl or optionally substituted alkyl; or one orboth of R′ and R″ forms a fused heterocyclic ring with aryl to which theN is attached to.

In some embodiments, each of D₁, D₂, D₃, and D₄ in formula IIa andformula IIb are each independently C₆₋₁₀ aryl or optionally substitutedC₆₋₁₀ aryl. The substituent(s) on the C₆₋₁₀ aryl may be selected fromthe group consisting of —NR′R″, —C₆₋₁₀ aryl-NR′R″, C₁₋₈ alkyl and C₁₋₈alkoxy, wherein R′ and R″ are independently selected from the groupconsisting of C₁₋₈ alkyl, C₁₋₈ alkoxy, C₆₋₁₀ aryl, C₆₋₁₀ aryl-C₁₋₈alkyl, C₆₋₁₀ aryl-C₁₋₈ alkoxy, and C₆₋₁₀ aryl-C(═O)R, wherein R isoptionally substituted C₁₋₈ alkyl, optionally substituted C₁₋₈ alkoxy oroptionally substituted C₆₋₁₀ aryl; or one or both of R′ and R″ forms afused heterocyclic ring with aryl to which the N is attached to.

In some embodiments, the chromophore is represented by formula IIa orformula IIb, wherein Het₂ is

provided that R_(a) and R_(b) are not both hydrogen, and D₁ and D₂ areindependently selected from the group consisting of:

In some embodiments, the chromophore is represented by formula IIa orformula IIb, wherein Het₂ is

provided that R_(a) and R_(b) are not both hydrogen.

In some embodiments, the chromophore is represented by formula IIa orformula IIb, wherein Het₂

and provided that D₁ and D₂ are independently selected from the groupconsisting of:

In some embodiments, the chromophore is represented by formula IIa orIIb, wherein Het₂ is

provided that D₁ and D₂ are not hydroxy or

and D₁ and D₂ do not comprise bromine.Formula III

Some embodiments provide a chromophore represented by formula IIIa andformula IIIb:

wherein Het₃ is selected from the group consisting of:

wherein X is selected from the group consisting of —N(A₀)-, —O—, —S—,—Se—, and —Te—.

Each A₀ of formula IIIa and formula IIIb is selected from the groupconsisting of hydrogen, optionally substituted alkyl, optionallysubstituted alkenyl, optionally substituted heteroalkyl, optionallysubstituted aryl, optionally substituted heteroaryl, optionallysubstituted amino, optionally substituted amido, optionally substitutedcyclic amido, optionally substituted cyclic imido, optionallysubstituted alkoxy, optionally substituted acyl, optionally substitutedcarboxy, and optionally substituted carbonyl. In some embodiments, A₀ isC₁₋₈ alkyl.

Each R_(a), R_(b), and R_(c), of formula IIIa and formula IIIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkyl, optionally substituted alkoxyalkyl, optionallysubstituted alkenyl, optionally substituted heteroalkyl, optionallysubstituted heteroalkenyl, optionally substituted aryl, optionallysubstituted arylalkyl, optionally substituted heteroaryl, optionallysubstituted cylcoalkyl, optionally substituted cycloalkenyl, optionallysubstituted cycloheteroalkyl, optionally substituted cycloheteroalkenyl,optionally substituted amino, optionally substituted amido, optionallysubstituted cyclic amido, optionally substituted cyclic imido,optionally substituted alkoxy, optionally substituted carboxy, andoptionally substituted carbonyl; or R_(a) and R_(b), or R_(b) and R_(c),or R_(a) and R_(c), together form an optionally substituted ring or anoptionally substituted polycyclic ring system, wherein each ring isindependently cycloalkyl, aryl, heterocyclyl, or heteroaryl.

In some embodiments, each R_(a), R_(b), and R_(c) is independentlyselected from the group consisting of hydrogen, optionally substitutedC₁₋₈ alkyl, optionally substituted C₆₋₁₀ aryl, and optionallysubstituted C₆₋₁₀ heteroaryl. In some embodiments, each R_(a), R_(b),and R_(c), of formula I are independently selected from the groupconsisting of hydrogen, C₁₋₈ alkyl, C₆₋₁₀ aryl, and C₆₋₁₀ heteroaryl,wherein C₁₋₈ alkyl, C₆₋₁₀ aryl, and C₆₋₁₀ heteroaryl may each beoptionally substituted by optionally substituted C₃₋₁₀ cycloalkyl,optionally substituted C₁₋₈ alkoxy, halo, cyano, carboxyl, optionallysubstituted C₆₋₁₀ aryl, optionally substituted C₆₋₁₀ aryloxy,

In some embodiments, R_(a) and R_(b), or R_(b) and R_(c), or R_(a) andR_(c), together form an optionally substituted ring system selected fromthe group consisting of:

Each R_(d) and R_(e) of formula IIIa and formula IIIb is independentlyselected from the group consisting of hydrogen, optionally substitutedalkyl, optionally substituted alkoxyalkyl, optionally substitutedalkenyl, optionally substituted heteroalkyl, optionally substitutedheteroalkenyl, optionally substituted aryl, optionally substitutedarylalkyl, optionally substituted heteroaryl, optionally substitutedcylcoalkyl, optionally substituted cycloalkenyl, optionally substitutedcycloheteroalkyl, optionally substituted cycloheteroalkenyl, optionallysubstituted amino, optionally substituted amido, optionally substitutedcyclic amido, optionally substituted cyclic imido, optionallysubstituted alkoxy, optionally substituted carboxy, and optionallysubstituted carbonyl; or R_(d) and R_(e) together form an optionallysubstituted ring or an optionally substituted polycyclic ring system,wherein each ring is independently cycloalkyl, aryl, heterocyclyl, orheteroaryl.

Each D₁, D₂, D₃, and D₄ of formula IIIa and formula IIIb isindependently selected from the group consisting of hydrogen, optionallysubstituted alkoxy, optionally substituted aryloxy, optionallysubstituted acyloxy, optionally substituted alkyl, optionallysubstituted aryl, optionally substituted heteroaryl, optionallysubstituted amino, amido, cyclic amido, and cyclic imido, -aryl-NR′R″,-ary-aryl-NR′R″, and -heteroaryl-heteroaryl-R′; wherein R′ and R″ areindependently selected from the group consisting of optionallysubstituted alkyl, optionally substituted alkenyl, and optionallysubstituted aryl; or one or both of R′ and R″ forms a fused heterocyclicring with aryl to which the N is attached to; provided that D₁ and D₂are not both hydrogen, and D₁ and D₂ are not optionally substitutedthiophene or optionally substituted furan.

In some embodiments, the chromophore is represented by formula IIIa orformula IIIb, wherein D₁ and D₂ are each independently selected from thegroup consisting of alkoxyaryl, -aryl-NR′R″, and -aryl-aryl-NR′R″;wherein R′ and R″ are independently selected from the group consistingof alkyl and aryl optionally substituted by alkyl, alkoxy, or —C(═O)R;wherein R is optionally substituted aryl or optionally substitutedalkyl; or one or both of R′ and R″ forms a fused heterocyclic ring witharyl to which the N is attached to.

In some embodiments, each of D₁, D₂, D₃, and D₄ in formula IIIa andformula IIIb are each independently C₆₋₁₀ aryl or optionally substitutedC₆₋₁₀ aryl. The substituent(s) on the C₆₋₁₀ aryl may be selected fromthe group consisting of —NR′R″, —C₆₋₁₀ aryl-NR′R″, C₁₋₈ alkyl and C₁₋₈alkoxy, wherein R′ and R″ are independently selected from the groupconsisting of C₁₋₈ alkyl, C₁₋₈ alkoxy, C₆₋₁₀ aryl, C₆₋₁₀ aryl-C₁₋₈alkyl, C₆₋₁₀ aryl-C₁₋₈ alkoxy, and C₆₋₁₀ aryl-C(═O)R, wherein R isoptionally substituted C₁₋₈ alkyl, optionally substituted C₁₋₈ alkoxy oroptionally substituted C₆₋₁₀ aryl; or one or both of R′ and R″ forms afused heterocyclic ring with aryl to which the N is attached to.

In some embodiments, the chromophore is represented by formula IIIa orformula IIIb, wherein Het₃ is

provided that D₁ and D₂ are independently selected from the groupconsisting of:

In some embodiments, the chromophore is represented by formula IIIa orformula IIIb, wherein Het₃ is

provided that D₁ and D₂ are independently selected from the groupconsisting of:

In some embodiments, the chromophore is represented by formula IIIa orformula IIIb, wherein Het₃ is

provided that D₁ and D₂ are not hydroxy or

and D₁ and D₂ do not comprise bromine.

In some embodiments, X in formula I, formula IIIa, and formula IIIb, isselected from the group consisting of —N(A₀)-, —S—, and —Se—.

In some embodiments, Z in formula I, formula IIa, and formula IIb, isselected from the group consisting of —N(R_(a))—, —S—, and —Se—.

In some embodiments, A₀ in formula I, formula IIa, formula IIb, formulaIIIa, and formula IIIB, is selected from the group consisting ofhydrogen, optionally substituted C₁₋₁₀ alkyl, optionally substitutedaryl, optionally substituted heteroaryl, and optionally substitutedalkoxyalkyl. In some embodiments, A₀ is selected from the groupconsisting of: hydrogen, methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, pentyl, hexyl,

In some embodiments, A₀ is hydrogen or C₁₋₈ alkyl. In some embodimentsA₀ is isobutyl. In some embodiments A is tert-butyl. In someembodiments, A₀ is

In some embodiments, A₀ is

In some embodiments, R_(a), R_(b), or R_(c), in formula I, formula IIa,formula IIb, formula IIIa, and formula IIIB, are independently selectedfrom the group consisting of hydrogen, optionally substituted C₁₋₁₀alkyl, optionally substituted aryl, optionally substituted heteroaryl,and optionally substituted alkoxyalkyl. In some embodiments R_(a) andR_(b), or R_(b) and R_(c), or R_(a) and R_(c), together form anoptionally substituted polycyclic ring system.

In some embodiments, R_(a), R_(b), or R_(c), in formula I, formula IIa,formula IIIb, formula IIIa, and formula IIIB, are independently selectedfrom the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, tert-butyl, pentyl, hexyl,

In some embodiments, R_(a) and R_(b), or R_(b) and R_(c), together formone of the following ring structures:

In some embodiments, D₁ and D₂ are each independently selected from thegroup consisting of the following structures:

In some embodiments, at least one of the L in formula I is selected fromthe group consisting of: 1,2-ethylene, acetylene, 1,4-phenylene,1,1′-biphenyl-4,4′-diyl, naphthalene-2,6-diyl, naphthalene-1,4-diyl,9H-fluorene-2,7-diyl, perylene-3,9-diyl, perylene-3,10-diyl, orpyrene-1,6-diyl, 1H-pyrrole-2,5-diyl, furan-2,5-diyl, thiophen-2,5-diyl,thieno[3,2-b]thiophene-2,5-diyl, benzo[c]thiophene-1,3-diyl,dibenzo[b,d]thiophene-2,8-diyl, 9H-carbozole-3,6-diyl,9H-carbozole-2,7-diyl, dibenzo[b,d]furan-2,8-diyl,10H-phenothiazine-3,7-diyl, and 10H-phenothiazine-2,8-diyl; wherein eachmoiety is optionally substituted.

With regard to L in any of the formulae above, the electron linkerrepresents a conjugated electron system, which may be neutral or serveas an electron donor itself. In some embodiments, some examples areprovided below, which may or may not contain additional attachedsubstituents.

Wavelength Conversion Luminescent Medium

The chromophores disclosed herein are useful and may be suitable forproviding a fluorescence film for use in improving long wavelengthconversion efficiency and provide high fluorescence quantum efficiency.The chromophores can provide a wavelength conversion luminescent mediumthat provides excellent light conversion effects. The wavelengthconversion luminescent medium receives as input at least one photonhaving a first wavelength, and provides as output at least one photonhaving a second wavelength which is longer (higher) than the firstwavelength.

The wavelength conversion luminescent medium comprises an opticallytransparent polymer matrix and at least one organic luminescent dyecomprising a chromophore disclosed herein. In some embodiments, thepolymer matrix is formed from a substance selected from the groupconsisting of polyethylene terephthalate, polymethyl methacrylate,polyvinyl butyral, ethylene vinyl acetate, ethylene tetrafluoroethylene,polyimide, amorphous polycarbonate, polystyrene, siloxane sol-gel,polyurethane, polyacrylate, and combinations thereof.

In some embodiments, the luminescent dye is present in the polymermatrix in an amount in the range of about 0.01 wt % to about 3 wt %,about 0.03 wt % to about 2 wt %, about 0.05 wt % to about 1 wt %, about0.1 wt % to about 0.9 wt %, or about 0.2 wt % to about 0.7 wt %. In anembodiment of the medium, the luminescent dye is present in the polymermatrix in an amount of about 0.5 wt %.

In some embodiments, the refractive index of the polymer matrix materialis in the range of about 1.4 to about 1.7, about 1.45 to about 1.65, orabout 1.45 to about 1.55. In some embodiments, the refractive index ofthe polymer matrix material is about 1.5.

In some embodiments, a wavelength conversion luminescent medium isfabricated into a thin film structure by (i) preparing a polymersolution with dissolved polymer powder in a solvent such astetrachloroethylene (TCE), cyclopentanone, dioxane, etc., at apredetermined ratio; (ii) preparing a luminescent dye containing apolymer mixture by mixing the polymer solution with the luminescent dyeat a predetermined weight ratio to obtain a dye-containing polymersolution, (iii) forming a dye/polymer thin film by directly casting thedye-containing polymer solution onto a glass substrate, then heattreating the substrate from room temperature up to 100° C. in 2 hours,completely removing the remaining solvent by further vacuum heating at130° C. overnight, and (iv) peeling off the dye/polymer thin film underthe water and then drying out the free-standing polymer film before use;(v) the film thickness can be controlled by varying the dye/polymersolution concentration and evaporation speed.

The luminescent thin film thickness may vary over a wide range. In someembodiments, the luminescent thin film thickness is between about 0.1 μmto about 1 mm, about 0.5 μm to about 1 mm, or about 1 μm to about 0.8mm. In some embodiments, the luminescent thin film thickness is betweenabout 5 μm to about 0.5 mm.

Wavelength conversion mediums are useful in various applications, suchas optical light collection systems, fluorescence-based solarcollectors, fluorescence-activated displays, and single-moleculespectroscopy, to name a few. The use of the organic wavelengthdown-shifting luminescent medium as disclosed herein, significantlyenhances the photoelectric conversion efficiency of photovoltaic devicesor solar cells by greater than 0.5% when applied directly to the lightincident surface of the device or encapsulated directly into the deviceduring fabrication.

Photovoltaic Module and Method

Another aspect of the invention provides a photovoltaic module for theconversion of solar light energy into electricity, the photovoltaicmodule comprises at least one photovoltaic device or solar cell, and awavelength conversion luminescent medium as described herein. The atleast one photovoltaic device or solar cell is adapted to convertincident solar light energy into electricity. The wavelength conversionluminescent medium is positioned such that the incident light passesthrough the wavelength conversion luminescent medium prior to reachingthe photovoltaic device or solar cell. The photovoltaic module utilizesthe wavelength conversion luminescent medium to enhance thephotoelectric conversion efficiency of a photovoltaic device.

Many of these photovoltaic devices or solar cells utilize materials onthe light incident side of the device which absorb certain wavelengthsof the solar spectrum, typically the shorter ultra violet (UV)wavelengths, instead of allowing the light to pass through to thephotoconductive material of the device. This UV absorption effectivelyreduces the efficiency of the device. The use of a down-shifting mediumin these photovoltaic devices and solar cells, when applied to the lightincident side of the device, causes the shorter wavelength light tobecome excited and re-emitted from the medium at a longer (higher) morefavorable wavelength, which can then be utilized by the photovoltaicdevice or solar cell, effectively enhancing the photoelectric conversionefficiency by allowing a wider spectrum of solar energy to be convertedinto electricity.

Another aspect of the disclosure is a method for improving theperformance of a photovoltaic device or solar cell comprising applying awavelength conversion luminescent medium directly onto the lightincident side of the solar cell or photovoltaic device.

Yet another aspect of the disclosure provides a method for improving theperformance of a photovoltaic device or solar cell, comprisingincorporating a wavelength conversion luminescent medium directly intothe photovoltaic device or solar cell during its fabrication, such thatthe luminescent medium is encapsulated between the photovoltaic deviceor solar cell and a cover substrate on the light incident side.

In some embodiments, the luminescent film is directly attached onto thelight incident surface of a solar cell. A photovoltaic device or solarcell in which a thin film wavelength conversion luminescent medium isdirectly attached to the light incident surface of the device. Arefractive index matching liquid or optical adhesive is applied betweenthe luminescent film and the light incident surface of the solar cell toensure better light out-coupling efficiency.

In some embodiments, a refractive index matching liquid or opticaladhesive is applied between the luminescent film and the front substrateof the solar cell to ensure better light out-coupling efficiency.

In some embodiments, the luminescent film is directly applied as theencapsulation layer during solar cell fabrication. The luminescent filmis encapsulated between the solar cell module and its front coversubstrate. A photovoltaic device or solar cell in which a thin filmwavelength conversion luminescent medium can be fabricated directly intothe module as the encapsulation layer between the optically transparentlight incident surface of the module and the photovoltaic device orsolar cell.

In some embodiments, the solar cell is a CdS/CdTe solar cell. In anotherembodiment the solar cell is a CIGS solar cell. In an embodiment thesolar cell is selected from the group consisting of an amorphous Siliconsolar cell, a microcrystalline Silicon solar cell, or a crystallineSilicon solar cell.

In some embodiments, the solar cell efficiency is measured with andwithout the thin film organic down-shifting luminescent medium under onesun irradiation (AM1.5G) by using a Newport solar simulator system. Theefficiency enhancement of the solar cell with the luminescent medium isdetermined by the equation below:Efficiency Enhancement=(η_(cell+lummescent film)−η_(cell))/η_(cell)*100%

In some embodiments, a crystalline Silicon solar cell is modified with awavelength conversion luminescent medium according to the methoddisclosed herein, and the efficiency enhancement is determined to begreater than about 0.2%. In an embodiment, the efficiency enhancement isdetermined to be greater than about 0.4%. In an embodiment, theefficiency enhancement is determined to be greater than about 0.5%. Inan embodiment, the efficiency enhancement is determined to be greaterthan about 0.8%. In an embodiment, the efficiency enhancement isdetermined to be greater than about 1.0%.

In some embodiments, a CdS/CdTe solar cell with an efficiency η_(cell)of 11.3%, which is similar to the efficiency level achieved in mostcommercially available CdS/CdTe cells, is modified with a wavelengthconversion luminescent medium according to the method disclosed herein,and the efficiency enhancement is determined to be greater than about2%.

In some embodiments, a CIGS solar cell with an efficiency η_(cell) of14.0%, which is slightly higher than the efficiency level achieved inmost commercially available CIGS cells, is modified with a wavelengthconversion luminescent medium according to the method disclosed herein,and the efficiency enhancement is determined to be greater than about6%.

In some embodiments, a photovoltaic device or solar cell comprises atleast one device selected from the group consisting of a CadmiumSulfide/Cadmium Telluride solar cell, a Copper Indium Gallium Diselenidesolar cell, an amorphous Silicon solar cell, a microcrystalline Siliconsolar cell, or a crystalline Silicon solar cell.

For purposes of summarizing aspects of the invention and the advantagesachieved over the related art, certain objects and advantages of theinvention are described in this disclosure. Of course, it is to beunderstood that not necessarily all such objects or advantages may beachieved in accordance with any particular embodiment of the invention.Thus, for example, those skilled in the art will recognize that theinvention may be embodied or carried out in a manner that achieves oroptimizes one advantage or group of advantages as taught herein withoutnecessarily achieving other objects or advantages as may be taught orsuggested herein.

Further aspects, features and advantages of this invention will becomeapparent from the examples which follow.

EXAMPLES

The embodiments will be explained with respect to certain embodimentswhich are not intended to limit the present invention. In the presentdisclosure, the listed substituent groups include both furthersubstituted and unsubstituted groups unless specified otherwise.Further, in the present disclosure where conditions and/or structuresare not specified, the skilled artisan in the art can readily providesuch conditions and/or structures, in view of the present disclosure, asa matter of routine experimentation guided by the present disclosure.

For each example compound, the maximum absorption and fluorescenceemission wavelength were measured in a solution and/or in a polymerfilm. For example, in a dichloromethane solution of the obtainedchromophore Compound 1(4,4′-(6,7-diethyl-2-isobutyl-2H-[1,2,3]triazolo[4,5-g]quinoxaline-4,9-diyl)bis(N,N-diphenylaniline)),the maximum absorption of the chromophore was 484 nm and the maximumfluorescence absorption was 616 nm upon 484 nm light illumination. In aPMMA (polymethyl methacrylate) film (having 0.3 wt % chromophore)comprising chromophore Compound 1, the maximum absorption of the filmwas 481 nm and the maximum fluorescence emission was 593 nm upon 481 nmlight illumination. The wavelength differences between maximumabsorption and maximum fluorescence is an improved property that isuseful for new optical light collection systems and fluorescence-basedsolar collectors.

Example Synthesis and Spectral Data

General Procedure for Preparation of Tosylates

Equimolar amounts of p-toluenesulfonic chloride, corresponding alcoholsand 1.2 equivalents of triethylamine were stirred in dichloromethaneovernight at room temperature. Work-up with water, drying with anhydrousMgSO₄, and concentration provided 95-98% pure tosylated alcohols whichwere used without purification in the synthesis of the compoundsdescribed below.

Intermediate A

Intermediate A was synthesized according to the following reactionscheme:

Benzothiadiazole (25 g, 184 mmol) was reacted overnight with 20.8 mLbromine (2.2 eq) in 400 mL of 48% HBr (in water) at 125-130° C. Aftercooling the reaction mixture (heavy suspension of reddish-brown solid)was poured into 1 liter of crushed ice and left to stir for 30 minutes.Filtration, washing with water, followed by washing with sodium sulfitesolution and water gave 4,7-dibromobenzothiadiazole as brick coloredneedles, (50.1 g, 92%, after drying in vacuum oven). This material wasused for nitration with fuming nitric acid in trifluoromethanesulfonicacid (TFMSA) as follows: nitric acid (10.0 mL) was added dropwise toTFMSA (150 g) which was cooled below 5° C. with intensive stirring(white solid formed). 4,7-Dibromobenzothiadiazole (as solid) was addedportionwise to the above reaction mixture and, after it becamehomogenous, the flask was placed in an oil bath and left to stir at 50°C. for 16-24 hours. The reaction was monitored by ¹³C NMR (110.4, 145.0,and 151.4 ppm). Pouring the solution into 500 mL of ice/water affordedIntermediate A (4,7-dibromo-5,6-dinitrobenzothiadiazole) as a yellowishsolid which was thoroughly washed with water and dried in vacuum oven(30.6 g, 94%).

Intermediate B

Intermediate B was synthesized according to the following reactionscheme:

4-Bromotriphenylamine (65.0 g, 200 mmol) was placed in a 500 ml drythree necked RB flask equipped with a magnetic stirring bar, lowtemperature thermometer and argon inlet. Tetrahydrofurane wastransferred to the reaction flask using a cannula (200 ml) and cooled ina dry-ice acetone bath to −78° C. and n-BuLi 91.6M in hexane (130 mL)was added dropwise over a period of 30 minutes. The reaction mixture wasleft to stir at the same temperature for 30 minutes at which timetributyltin chloride (65.0 mL) was added dropwise over 30 minutes. Thereaction was left to stir overnight, after which the reaction wasallowed to warm to room temperature. The solution was poured intoice-cold water (approximately 500 mL) and extracted using diethyl ether(2×250 mL). The organic layer was dried with MgSO₄ and the solvent wasremoved by evaporation to give 106.5 g of Intermediate B as yellowishoil, by ¹H NMR approximately 95% pure.

Intermediate C

Intermediate C was synthesized according to the following reactionscheme:

Step 1: A mixture of Intermediate A (3.84 g, 10 mmol), Intermediate B(10.7 g, mmol), and Bis(triphenylphosphine)palladium(II) chloride (1.40g, 2.0 mmol) in tetrahydrofurane was stirred and heated under argon at70° C. for 5 hours. The solvent was removed and MeOH was added (100 mL)to the residue. The purple solid was separated by filtration, washedwith MeOH, and dried to give4,4′-(5,6-dinitrobenzo[c][1,2,5]thiadiazole-4,7-diyl)bis(N,N-diphenylaniline)(7.0 g) as purple solid.

Step 2: A mixture of the above crude4,4′-(5,6-dinitrobenzo[c][1,2,5]thiadiazole-4,7-diyl)bis(N,N-diphenylaniline)(calculated for 10 mmol) and iron dust (5.6 g, 100 mmol) was heated inglacial acetic acid (100 mL) with 5% of water (to prevent formation ofside product, imidazole) at 110° C. for 2 hours. The solution was pouredinto ice-water (200 mL) and the resulting solid was separated byfiltration, washed with water and dried. After filtering through 2layers of silica gel (to remove particles of iron) using ethylDCM/hexane (3:2) and concentration, Intermediate C(4,7-bis(4-(diphenylamino)phenyl)benzo[c][1,2,5]thiadiazole-5,6-diamine)was collected as a light brown solid (4.50 g, 68%, after 2 steps). ¹HNMR (400 MHz, CDCl₃): δ 7.44 (d, J=8.6 Hz, 4H), 7.16-7.30 (m, 20H), 7.44(t, J=6.3 Hz, 4H).

Intermediate D

Intermediate D was synthesized according to the following reactionscheme:

Step 1: A mixture of benzotriazole (11.91 g, 100 mmol),1-iodo-2-methylpropane (13.8 mL, 120 mmol), potassium carbonate (41.46g, 300 mmol), and dimethylformamide (200 mL) was stirred and heatedunder argon at 40° C. for 2 days. The reaction mixture was poured intoice/water (1 L) and extracted with toluene/hexanes (2:1, 2×500 mL). Theextract was washed with 1 N HCl (2×200 mL) followed by brine (100 mL).The extract was then dried over anhydrous MgSO₄, and the solvent wasremoved under reduced pressure. The residue was triturated with hexane(200 mL) and set aside at room temperature for 2 hours. The precipitatewas separated and discarded, and the solution was filtered through alayer of silica gel (200 g). The silica gel was washed withhexane/dichloromethane/ethyl acetate (37:50:3, 2 L). The filtrate andwashings were combined, and the solvent was removed under reducedpressure to yield 2-isobutyl-2H-benzo[d][1,2,3]triazole (8.81 g, 50%yield) as an oily product. ¹H NMR (400 MHz, CDCl₃): δ 7.86 (m, 2H,benzotriazole), 7.37 (m, 2H, benzotriazole), 4.53 (d, J=7.3 Hz, 2H,i-Bu), 2.52 (m, 1H, i-Bu), 0.97 (d, J=7.0 Hz, 6H, i-Bu).

Step 2: A mixture of 2-isobutyl-2H-benzo[d][1,2,3]triazole (8.80 g, 50mmol), bromine (7.7 mL, 150 mmol) and 48% HBr (50 mL) was heated at 130°C. for 24 hours under a reflux condenser connected with an HBr trap. Thereaction mixture was poured into ice/water (200 mL), treated with 5 NNaOH (100 mL) and extracted with dichloromethane (2×200 mL). The extractwas dried over anhydrous magnesium sulfate, and the solvent was removedunder reduced pressure. A solution of the residue inhexane/dichloromethane (1:1, 200 mL) was filtered through a layer ofsilica gel and concentrated to yield4,7-dibromo-2-isobutyl-2H-benzo[d][1,2,3]triazole, (11.14 g, 63% yield)as an oil that slowly solidified upon storage at room temperature. ¹HNMR (400 MHz, CDCl₃): δ 7.44 (s, 2H, benzotriazole), 4.58 (d, J=7.3 Hz,2H, i-Bu), 2.58 (m, 1H, i-Bu), 0.98 (d, J=6.6 Hz, 6H, i-Bu).

Step 3: 4,7-dibromo-2-isobutyl-2H-benzo[d][1,2,3]triazole (17.8 g, 53mmol) was added at 0-5° C. to a premixed fuming HNO₃ (7.0 mL) and TFMSA(110 g) portionwise and after approximately 10 minutes the reactionmixture was placed in an oil bath and heated at 55° C. for 8 hours. Thesolution was then cooled by pouring into 500 mL of ice/water. The solidobtained was thoroughly washed with water, followed by MeOH and dried ina vacuum oven to yield Intermediate D(4,7-dibromo-2-isobutyl-5,6-dinitro-2H-benzo[d][1,2,3]triazole) asyellowish solid (20.4 g, 91%). ¹H NMR (400 MHz, CDCl₃): δ 4.66 (δ, J=7.2Hz, 2H, i-Bu), 2.60 (m, 1H, i-Bu), 1.01 (d, J=7.0 Hz, 6H, i-Bu).

Intermediate E

Intermediate E was synthesized according to the following reactionscheme:

Step 1: In a three necked reaction flask equipped with argon inlet andmagnetic stirring bar, was placed THF (100 mL), Intermediate B (31.1 g,30 mmol), and argon was bubbled through for approximately 10 minutesbefore bis(triphenylphosphine)palladium(II) chloride (10% molar perIntermediate B, 1.80 g, 2.5 mmol) was added. The reaction was stirredunder argon for 10 minutes before Intermediate D (10.6 g, 25 mmol) wasadded in one portion. The reaction mixture was refluxed for 22 hours.The reaction was monitored by LCMS and TLC. The reaction was cooled andMeOH (200 mL) was added while stirring. A dark orange color solid wasformed which was separated by filtration, washed with MeOH, and dried togive4,4′-(2-isobutyl-5,6-dinitro-2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(N,N-diphenylaniline)(11.5 g, 62%, purity by LCMS 86%).

Step 2: A mixture of4,4′-(2-isobutyl-5,6-dinitro-2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(N,N-diphenylaniline)(6.0 g, 8.0 mmol) and iron powder (4.5 g, 80 mmol) was heated andstirred in glacial acetic acid (100 mL) at 130° C. for 2 hours. Thereaction was monitored by LCMS and TLC. The reaction was cooled andpoured into water to yield yellow solid which was separated byfiltration, washed with water and dried to give Intermediate E(4,7-bis(4-(diphenylamino)phenyl)-2-isobutyl-2H-benzo[d][1,2,3]triazole-5,6-diamine)(4.6 g, 66%, purity by LCMS 82%).

Compound 1

Synthesis of Compound 1 was performed according to the following scheme:

Intermediate E (crude, 990 mg, calculated for 1.2 mmol) and1,4-hexanedione (170 mg, 1.5 mmol) was stirred in a mixture of aceticacid and DCM (20 mL, 1:1) at room temperature for one hour. EvaporatingDCM and adding water (50 mL) provided a red solid which was separated byfiltration, washed with water, followed by MeOH, and dried. Columnchromatography (DCM/Hexane, 1:1) gave Compound 1(4,4′-(6,7-diethyl-2-isobutyl-2H-[1,2,3]triazolo[4,5-g]quinoxaline-4,9-diyl)bis(N,N-diphenylaniline))as a red solid (590 mg, 64%). ¹H NMR (400 MHz, CDCl₃): δ 8.06 (d, J=8.8Hz, 4H), 7.24-7.29 (m, 20H), 7.05 (t, J=7.2 Hz, 4H), 4.67 (d, J=7.3 Hz,2H), 3.00 (q, J=7.3 Hz, 4H), 2.61-2.67 (m, 1H), 1.39 (t, J=6.5 Hz, 6H),1.01 (d, J=6.5 Hz, 6H). UV-vis spectrum: λ_(max)=484 nm(dichloromethane), 481 nm (PMMA film). Fluorimetry: λ_(max)=616 nm(dichloromethane), 593 nm (PMMA film).

Compound 2

Synthesis of Compound 2 was performed according to the following scheme:

Intermediate E (5.54 g, 8 mmol) was dissolved in 50 mL of THF (forsolubility) and 50 mL of acetic acid was added. The mixture was thencooled in an ice/water bath before 12 mL of 1M solution of NaNO₂ inwater was added. After 10 minutes the reaction was complete. Dilutingwith 400 mL of water afforded an orange color solid which was separatedby filtration, washed and dried to give Compound 2,4,4′-(6-isobutyl-1,6-dihydrobenzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-4,8-diyl)bis(N,N-diphenylaniline)as an orange solid (2.72 g, 48%). ¹H NMR (400 MHz, CDCl₃): δ 8.5 (bs,1H), 7.9 (bs, 1H), 7.2-7.3 (m, 24H), 7.08 (t, J=7.3 Hz, 4H), 4.65 (d,J=7.4 Hz, 2H), 2.64 (m, 1H), 1.01 (d, J=6.5 Hz, 6H). UV-vis spectrum:λ_(max)=474 nm (dichloromethane), 474 nm (PMMA film). Fluorimetry:λ_(max)=575 nm (dichloromethane), 555 nm (PMMA film).

Compound 3

Synthesis of Compound 3 was performed according to the following scheme:

1.70 g of4,4′-(6-isobutyl-1,6-dihydrobenzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-4,8-diyl)bis(N,N-diphenylaniline(Compound 2), calculated for 2.5 mmol was dissolved in DMF (30 mL).Potassium carbonate (2.80 g, 20 mmol) was added, followed by2-butoxyethyl 4-methylbenzenesulfonate (1.36 g, 5 mmol) and the reactionmixture was heated at 125° C. for 50 minutes. The solution was rotavapedand the residue was triturated with MeOH. The reddish-brown solid wasseparated, washed with MeOH and dried. Column chromatography (silicagel, DCM/Hex-3:2) provided Compound 3(4,4′-(2-(2-butoxyethyl)-6-isobutyl-1,2,3,6-tetrahydrobenzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-4,8-diyl)bis(N,N-diphenylaniline))as a red solid (1.62 g, 80%). ¹H NMR (400 MHz, CDCl₃): δ 8.60 (d, J=8.7Hz, 4H), 7.20-732 (m, 20H), 7.06 (t, J=7.3 Hz, 4H), 5.02 (t, J=5.8 Hz,2H), 4.66 (d, J=7.4 Hz, 2H), 4.20 (t, J=6.0 Hz, 2H), 3.48 (t, J=6.6 Hz,2H), 2.66 (d, J=6.9 Hz, 2H), 1.50 (m, 2H), 1.23 (m, 2H), 1.00 (m, 2H),□1.03 (d, J=6.6 Hz, 6H), 0.78 (t, J=7.7 Hz). UV-vis spectrum:λ_(max)=517 nm (dichloromethane), 512 nm (PMMA film). Fluorimetry:λ_(max)=615 nm (dichloromethane), 606 nm (PMMA film).

Compound 4

Synthesis of Compound 4 was performed according to the following scheme:

Intermediate C (6.5 g, 10 mmol) was dissolved in a mixture of THF andacetic acid (25 mL+25 mL) in a beaker and vigorously stirred inice/water bath to keep the temperature below 10° C. The solution ofNaNO₂ (0.83 g) in 10 mL of water was prepared and after cooling in thesame bath was added portionwise to the reaction mixture. After 10minutes, the mixture was removed from the cooling bath and left to stirat room temperature for one hour (monitored by TLC, Hexane/EA-4:1). Astrong purple color of the product formed in comparison to yellow colorof the starting material. The crude reaction mixture was partitionedbetween water and DCM, and the organic layer was washed with water andthe solvent removed. The solid residue was triturated with MeOH and thedark purple solid was separated by filtration and dried to give Compound4,(4,4′-1H-[1,2,3]triazolo[4′,5′:4,5]benzo[1,2-c][1,2,5]thiadiazole-4,8-diyl)bis(N,N-diphenylaniline))(5.9 g, 80% pure by LCMS) which was used without further purificationfor the next step. UV-vis spectrum: λ_(max)=550 nm (dichloromethane),Fluorimetry: λ_(max)=707 nm (dichloromethane).

Compound 5

Synthesis of Compound 5 was performed according to the following scheme:

The Compound 4 crude material (3.32 g, 5 mmol) was dissolved in 20 mL ofDMF. 2-ethylhexyl 4-methylbenzenesulfonate (1.71 g, 7.0 mmol) was addedfollowed by K₂CO₃ (1.38 g, 10 mmol). The reaction mixture was stirred at80° C. (oil bath) for 4 hours. The reaction was monitored by TLC, and astrong blue color was observed. After reaction was accomplished it waspoured into water and the resulting precipitate was separated, washedwith water, followed by MeOH, and dried in a vacuum oven. Purificationby column chromatography (Hexane/DCM, 1:1) afforded Compound 5(4,4′-(6-(2-ethylhexyl)-1H-[1,2,3]triazolo[4′,5′:4,5]benzo[1,2-c][1,2,5]thiadiazole-4,8-diyl)bis(N,N-diphenylaniline))as dark blue solid (1.42 g, 36%). ¹H NMR (400 MHz, CDCl₃): δ 8.37 (J=8.8Hz, 4H), 7.24-7.31 (m, 20H), 7.06-7.09 (t, J=7.0 Hz, 4H), 4.79 (d, J=7.3Hz, 2H), 2.35 (m, 1H), 1.2-1.4 (m, 8H), 0.96 (t, J=7.3 Hz, 3H), 0.85 (t,J=7.0 Hz, 3H). UV-vis spectrum: λ_(max)=604 nm (dichloromethane), 613 nm(PMMA film). Fluorimetry: λ_(max)=755 nm (dichloromethane), 695 nm (PMMAfilm).

Compound 6

Synthesis of Compound 6 was performed according to the following scheme:

Compound 6 was prepared from Intermediate C by cyclization withN-thionyl aniline (0.5 mL/1 mmol) in pyridine at 80° C. overnight in thepresence of trimethylsilyl chloride (2.0 mL/1 mmol). After work-up andpurification by column chromatography with DCM/hexane (3:2) the mixturewas reacted with valeryl chloride (10 eq) in DCM in the presence of zincchloride (10 eq). The reaction mixture was then refluxed for four hours(monitored by LCMS). After cooling the reaction mixture was poured ontoice/cold water and neutralized with sodium bicarbonate. The organiclayer was washed with water, dried (magnesium sulfate) and the solventevaporated. Then, column chromatography with hexane/ethyl acetateallowed separation of the main isomer to obtain Compound 6. ¹H NMR (400MHz, CDCl₃): δ 8.25 (d, J=8.8 Hz, 4H), 7.87 (d, J=8.8 Hz, 4H), 7.37 (m,8H), 7.20-7.29 (m, 10H), 2.92 (m, 4H), 1.74 (m, 4H), 1.41 (m, 4H), 0.95(t, J=7.3 Hz). UV-vis spectrum: λ_(max)=667 nm (dichloromethane),Fluorometry: λ_(max)=814 nm (dichloromethane).

Intermediate D-2

Synthesis of Intermediate D-2 was performed according to the followingscheme:

Intermediate D-2 was prepared similar to the procedure for IntermediateD, except that neopentyl tosylate was used instead of1-iodo-2-methylpropane and potassium carbonate. ¹H NMR for IntermediateD-2 (400 MHz, CDCl₃): δ 7.53 (d, J=8.8 Hz, 4H), 7.29 (t, J=8.4 Hz, 8H),7.20 (d, J=8.4 Hz, 12H), 7.05 (t, J=7.0 Hz, 4H), 4.38 (s, 2H), 0.99 (s,9H).

Intermediate E-2

Synthesis of Intermediate E-2 was performed according to the followingscheme:

Intermediate E-2 was prepared similar to the procedure for IntermediateE. ¹H NMR for nitro intermediate (400 MHz, CDCl₃): δ 4.66 (s, 2H), 1.08(s, 9H). ¹H NMR for Intermediate E-2, 7.43 (d, J=8.8 Hz, 4H), 7.31 (t,J=7.0 Hz, 8H), 7.20 (d, J=−8.4 Hz, 8H), 7.11 (t, J=8.8 Hz, 4H), 4.57 (s,2H), 1.02 (s, 9H).

Compound 7

Synthesis of Compound 6 was performed according to the following scheme:

Compound 7 was prepared following the same sequence of reaction as forCompound 2, except Intermediate E-2 was used instead of Intermediate E.¹H NMR for Compound 6 (400 MHz, CDCl₃): δ 8.0-8.5 (bs, 4H), 7.17-7.35(m, 20H), 7.02-7.12 (bs, 4H), 4.66 (s, 2H), 1.11 (s, 9H).

Compound 8

Synthesis of Compound 8 was performed according to the followingprocedures:

Compound 8 was prepared from 870 mg of Compound 4 and benzylbromide (1.0mL, 8.4 mmol). The reaction mixture was heated in DMF (20 mL) in thepresence of potassium carbonate (1.4 g, 10 mmol) for two hours at 130°C. The reaction was monitored by TLC, and a substance with a purplecolor of lower polarity than the blue starting material was formed.After cooling the reaction mixture was poured into ice-cold water andleft to stir. A solid was obtained, which was separated, and then washedwith water, followed by methanol, and dried. Column chromatography(silica gel, DCM/Hexane—2:1) produced Compound 7 as a purple solid (Bt-1isomer, 510 mg, yield 56%). ¹H NMR (400 MHz, CDCl₃): δ 8.36 (d, J=8.8Hz, 2H), 7.11-7.34 (m, 29H), 6.64 (d, J=6.6 Hz, 2H), 5.81 (s, 2H). δ9.15. UV-vis spectrum: λ_(max)=534 nm (dichloromethane), Fluorometry:λ_(max)=699 nm (dichloromethane).

Compound 9

Synthesis of Compound 9 was performed according to the followingprocedures:

Compound 8 (500 mg, 0.66 mmol) was reacted with 1.0 mL of drytert-butanol in 25 mL of trifluoroacetic acid at reflux for six hours.The reaction was monitored by TLC (different color and polarity).Evaporation of TFA and co-evaporation with toluene followed. Stirringwith water provided a purple solid which was separated and dried.Purification by column chromatography (DCM/hexane—3:2) gave Compound 9(Bt-1 isomer, 160 mg, yield 25%) as purple solid. ¹H NMR (400 MHz,CDCl₃): δ 8.33 (d, J=8.8 Hz, 2H), 7.10-7.40 (m, 25H), 6.64 (d, J=6.6 Hz,2H), 5.81 (s, 2H), 1.34 (s, 36H). δ 9.15 UV-vis spectrum: λmax=551 nm(dichloromethane), Fluorometry: λmax=697 nm (dichloromethane). λmax=798nm (dichloromethane).

Compound 10

Synthesis of Compound 10 was performed according to the followingprocedures:

Compound 10 was prepared from Compound 5 following a similar procedureas was used for Compound 9. Purification was performed by columnchromatography (DCM/hexane—1:1) to obtain Compound 10 (Bt-2 isomer).UV-vis spectrum: λ_(max)=627 nm (dichloromethane), Fluorometry:λ_(max)=789 nm (dichloromethane).

Compound 11

Synthesis of Compound 11 was performed according to the followingprocedures:

Compound 11 was prepared similarly to Compound 9 except 4-fluorobenzylbromide was used instead of tert-butanol. Compound 11 was obtained (Bt-1isomer). ¹H NMR (400 MHz, CDCl₃): δ 8.28 (d, J=8.8 Hz, 2H), 7.84 (d,J=2H), 7.74 (m, 2H), 7.0-7.4 (m, 22H), 2.22 (t, J=8.8 Hz, 2H), 6.48 (m,2H), 5.28 (s, 2H). UV-vis spectrum: λ_(max)=585 nm (dichloromethane),Fluorometry: λ_(max)=655 nm (dichloromethane).

Compound 12

Synthesis of Compound 12 was performed according to the followingprocedures:

Compound 12 was prepared similarly to Compound 4 but 2-butoxy-ethanoltosylate (2 eq, prepared according to general procedure) was usedinstead of tert-butanol. The reaction was carried out for 8 hours at130° C. After work-up and purification, Compound 12 was isolated as apurple solid (600 mg, yield 35%—Bt-1 isomer). ¹H NMR (400 MHz, CDCl₃): δ8.34 (d, J=8.8 Hz, 2H), 7.46 (d, J=8.8 Hz, 2H), 7.2-7.35 (m, 20H), 4.68(t, J=6.3 Hz, 2H), 3.56 (t, J=6.1 Hz, 2H), 3.26 (t, J=6.4 Hz, 2H),1.36-1.40 (m, 2H), 1.115-1.20 (m, 2H), 0.77 (t, J=7.7 Hz, 3H). UV-visspectrum: λ_(max)=536 nm (dichloromethane), Fluorometry: λ_(max)=690 nm(dichloromethane).

Compound 13

Synthesis of Compound 13 was performed according to the followingprocedures:

Compound 4 (330 mg, 0.5 mmol) was reacted with tosylate of triethyleneglycol monomethyl ether (640 mg, 2 mmol) in the presence of potassiumcarbonate (0.7 g, 5 mmol) in dry DMF (10 mL) at 130° C. for two hours.The reaction was monitored by TLC and LCMS. The reaction mixture waspoured into water and extracted with DCM, and then dried (MgSO₄anh.) androtavaped. Column chromatography (silica gel/DCM and gradually up to2.5% ethyl acetate) yielded pure Compound 12 as a dark navy solid (320mg, yield 78%, of pure Bt-2 isomer). ¹H NMR (400 MHz, CDCl₃): δ 8.36 (d,J=8.8 Hz, 4H), 7.22-7.33 (m, 20H), 7.08 (t, J=7.3 Hz, 4H), 5.06 (t,J=5.6 Hz, 2H), 4.30 (t, J=5.8 Hz, 2H), 3.66-3.68 (m, 2H), 3.56-3.58 (m,2H), 3.49-3.52 (m, 2H), 3.36-3.39 (m, 2H), 3.25 (s, 3H). UV-visspectrum: λ_(max)=616 nm (dichloromethane), Fluorometry: λ_(max)=758 nm(dichloromethane).

Compound 14

Synthesis of Compound 14 was performed according to the followingprocedures:

Compound 4 (660 mg, 1 mmol) was reacted according to the procedure forCompound 5 but with tosylate of cyclohexylmethyl alcohol (prepared as ingeneral procedure, 1.1 g, 5 eq) in dry DMF (10 mL) at 120° C. for 1hour. The reaction was monitored by TLC (starting material violet color,product dark blue). After work-up and column chromatography Compound 14was obtained as a dark blue solid (320 mg, yield 42%, Bt-2 isomer). ¹HNMR (400 MHz, CDCl₃): δ 8.37 (d, J=8.8 Hz, 4H), 4.22-4.33 (m, 20H), 7.08(t, J=7.3 Hz, 4H), 4.70 (d, J=7.4 Hz, 2H), 2.33 (m, 1H), 1.66-1.76 (m,4H), 1.11-1.28 (m, 6H).). UV-vis spectrum: λ_(max)=612 nm(dichloromethane), Fluorometry: λ_(max)=739 nm (dichloromethane).

Compound 15

Synthesis of Compound 15 was performed according to the followingprocedures:

Compound 15 was prepared similarly to Compound 14. UV-vis spectrum:λ_(max)=612 nm (dichloromethane), Fluorometry: λ_(max)=696 nm(dichloromethane).

Compound 16

Synthesis of Compound 16 was performed according to the followingprocedures:

Compound 16 was prepared from the Bt-1 isomer of Compound 5 using areaction procedure similar to that of Compound 9. The reaction wasmonitored by TLC (initially blue starting material, later purple productof lower polarity). Purified by column chromatography (in hexane/ethylacetate—4:1), to yield Compound 16. ¹H NMR (400 MHz, CDCl₃) Bt-1 isomer:δ 8.31 (d, J=8.8 Hz, 2H), 8.20 (d, J=8.8 Hz, 2H), 7.71 (d, J=8.8 Hz,2H), 7.41 (d, J=8.4 Hz, 2H), 7.14-7.33 (m, 20H), 3.48 (d, J=5.5 Hz, 2H),1.2-1.7 (m, 14H), 1.32 (s, 18H). UV-vis spectrum: λ_(max)=546 nm(dichloromethane), Fluorometry: λ_(max)=685 nm (dichloromethane).

Intermediate B-3

Synthesis of Intermediate B-3 was performed according to the followingscheme:

Intermediate B-3 was prepared similarly to the procedure used forIntermediate B.

Intermediate E-3

Synthesis of Intermediate E-3 was performed according to the followingscheme:

Intermediate E-3 was prepared similarly to the procedure used forIntermediate E, except that Intermediate B-3 was used instead ofIntermediate B.

Compound 17

Synthesis of Compound 17 was performed according to the followingscheme:

Compound 17 was prepared from Intermediate E-3 by reaction with benzil(1.2 eq) in DCM in the presence of acetic acid at room temperature forone hour. Column Chromotography (DCM/hexane—2:1) yielded Compound 17 asa red solid. ¹H NMR (400 MHz, CDCl₃) δ 8.04 (d, J=8.8 Hz, 4H), 7.97 (d,J=7.3 Hz, 2H), 7.65 (m, 4H), 7.52 (t, J=7.7 Hz, 2H), 7.30 (m, 4H), 7.19(d, J=8.8 Hz, 6H), 7.12 (d, J=8.8 Hz, 4H), 6.87 (d, J=8.8 Hz, 8H), 4.68(d, J=7.3 Hz, 2H), 3.72 (d, J=6.2 Hz, 8H), 2.66 (m, 1H), 2.08 (m, 4H),1.04 (2 doublets overlapped, 30H). UV-vis spectrum: λ_(max)=553 nm(dichloromethane), Fluorometry: λ_(max)=688 nm (dichloromethane).

Intermediate B-4

Synthesis of Intermediate B-4 was performed according to the followingscheme:

Intermediate B-4 was prepared similarly to the procedure used forIntermediate B. To a solution of tetrahydroquinoline and benzotriazolein ethanol, formaldehyde, 37% in water, was added portionwise whilestirring. After one hour heavy precipitate of Intermediate F was formed,which was separated, washed with ethanol, and dried.

To a solution of Intermediate F in toluene, Grignard reagent (solutionin ether) was added portionwise (1.2 eq) and the reaction mixture wasleft to stir at room temperature for 24 hours. The reaction wasmonitored by TLC (Hexane/Ethyl Acetate-4:1). Then, the reaction wasworked-up with water, dried (MgSO4 anhydrous), evaporated, and columnchromatography yielded Intermediate G as oil (10.8 g, 64%). ¹H NMR (400MHz, CDCl₃): δ 7.03 (t, J=7.4 Hz, 1H), 6.92 (d, J=7.0 Hz, 1H), 6.50-6.57(m, 2H), 3.25 (t, J=5.5 Hz, 2H), 3.21 (t, J=7.7 Hz, 2H), 2.74 (t, J=6.2Hz, 2H), 1.93 (m, 2H), 1.56 (m, 2H), 1.33 (m, 4H), 0.90 (t, J=7.0 Hz,3H).

Intermediate G was brominated with NBS (1 eq) at room temperature inchloroform for one hour. For work-up, hexane was added, and the solidwas disposed, filtered, and then the filtrate was washed with water, anddried to give Intermediate H as an oil, (yield 72%). ¹H NMR (400 MHz,CDCl₃): δ 7.08 (dd, J=8.8 and 2.6 Hz, 1H), 7.01 (d, J=2.6 Hz, 1H), 6.39(d, J=8.8 Hz, 1H), 3.24 (t, J=5.5 Hz, 2H), 3.18 (t, J=7.7 Hz, 2H), 2.70(t, J=6.4 Hz, 2H), 1.90 (m, 2H), 1.54 (m, 2H), 1.30 (m, 4H), 0.90 (t,J=7.3 Hz, 3H).

Intermediate H was lithiated with n-BuLi (1.1 eq) and reacted withtributyltin chloride (1.15 eq) at −78 C and later left overnight at roomtemperature. The mixture was extracted with ether, washed with water anddried to obtain crude product which was used directly for the next step.Intermediate B-4 was obtained as a yellowish oil. Yield approximately100% but 80% pure by LCMS. ¹H NMR (400 MHz, CDCl₃): 7.11 (d, J=7.7 Hz,1H), 6.98 (s, 1H), 6.54 (d, J=6.1 Hz, 1H), 3.25 (t, J=5.9 Hz, 2H), 3.20(t, J=7.7 Hz, 2H), 2.97 (t, J=6.2 Hz, 2H), 1.93 (m, 2H), 1.54 (m, 8H),1.30 (m, 10H), 0.90 (t, J=7.3 Hz, 3H), 0.88 (t, J=7.3 Hz, 9H).

Intermediate C-4

Synthesis of Intermediate C-4 was performed according to the followingscheme:

Intermediate C-4 was prepared similarly to the procedure used forIntermediate C, except that Intermediate B-4 was used instead ofIntermediate B.

Compound 18

Synthesis of Compound 18 was performed according to the followingscheme:

Compound 18 was prepared according to the procedure for Compound 4except that Intermediate C-4 was used instead of Intermediate C. Columnchromatography with DCM followed by 5% ethyl acetate in DCM yielded pureCompound 18 as a dark blue solid. ¹H NMR (400 MHz, CDCl₃): δ 8.13-8.30(2bs, 2H), 7.51-7.69 (2bs, 2H), 6.76 (d, J=8.1 Hz, 2H), 3.39 (m, 4H),3.32 (m, 4H), 2.90 (bs, 4H), 2.01 (m, 4H), 1.58-1.70 (m, 4H), 1.30-1.40(m, 8H), 1.13 (m, 4H), 0.93 (t, J=7.0 Hz, 6H). UV-vis spectrum:λ_(max)=614 nm (dichloromethane), Fluorometry: λ_(max)=777 nm(dichloromethane).

Compound 19

Synthesis of Compound 19 was performed according to the followingscheme:

Compound 19 was obtained from Compound 18 by alkylation with methylmethanesulfonate in the presence of potassium carbonate in DMF at 65° C.for 3 hours. Work-up with water, extraction with ethyl acetate, drying,and evaporation of the solvent gave crude product which was purified bycolumn chromatography (silica gel-hexane/ethyl acetate-4:1) to give darkblue oily product, Compound 19. UV-vis spectrum: λ_(max)=633 nm(dichloromethane), Fluorometry: λ_(max)=769 nm (dichloromethane).

Compound 20

Synthesis of Compound 20 was performed according to the followingscheme:

Compound 20 was obtained from Compound 18 by alkylation with2-ethylhexyl-4-methylbenzenesulfonate in DMF, at 80° C. in DMF in thepresence of potassium carbonate. Work-up followed the same procedure asthat of Compound 5, to yield Compound 20. UV-vis spectrum: λ_(max)=667nm (dichloromethane), Fluorometry: λ_(max)=812 nm (dichloromethane).

Compound 21

Synthesis of Compound 21 was performed according to the followingscheme:

Compound 21 was prepared from Intermediate C-4 by reaction with benzyl(1.2 eq) in DCM in the presence of acetic acid at room temperature forone hour. Column chromatography (DCM/hexane-2:1) afforded pure Compound21 as a greenish-blue solid. ¹H NMR (400 MHz, CDCl₃): δ 7.84 (d, J=8.4Hz, 2H), 7.77 (s, 2H), 7.67 (d, J=6.6 Hz, 4H), 7.25 (m, 6H), 6.80 (d,J=8.6 Hz, 2H), 3.39 (m, 8H), 2.96 (t, J=6.0 Hz, 4H), 2.06 (m, 4H), 1.69(m, 4H), 1.39 (m, 8H), 0.94 (t, J=6.8 Hz, 6H). UV-vis spectrum:λ_(max)=686 nm (dichloromethane), Fluorometry: λ_(max)=817 nm(dichloromethane).

Compound 22

Synthesis of Compound 22 was performed according to the followingscheme:

Compound 22 was prepared from Intermediate C-4 by reaction with benzoylchloride (1.2 eq) in toluene at reflux for two hours. Work-up and columnchromatography (DCM only, top spot) produced pure purple color Compound22. ¹H NMR (400 MHz, CDCl₃): δ 9.42 (bs, 2H), 8.11 (m, 4H), 8.03 (bs,2H), 7.51 (m, 6H), 6.77 (bs, 2H). UV-vis spectrum: λ_(max)=541 nm(dichloromethane), Fluorometry: λ_(max)=687 nm (dichloromethane).

Compound 23

Synthesis of Compound 23 was performed according to the followingscheme:

Compound 23 was obtained by alkylation of Compound 22 under standardconditions. The product was characterized only by TLC and LCMS, due tothe small amount obtained. UV-vis spectrum: λ_(max)=686 nm(dichloromethane), Fluorometry: λ_(max)=817 nm (dichloromethane).

Compound 24

Synthesis of Compound 24 was performed according to the followingscheme:

Compound 24 was obtained from Intermediate C-4 by reaction withphenanthrenequinone (1.2 eq) in DCM in the presence of acetic acid (20%by volume). The reaction mixture was left at room temperature overnight.DCM was removed by evaporation and the residue triturated with water.The solid obtained was separated, washed with methanol, dried, andpurified by column chromatography (DCM/hexane, 1:1) to give a dark blueproduct, Compound 24. ¹H NMR (400 MHz, CDCl₃): δ 9.11 (d, J=7.7 Hz, 2H),8.43 (d, J=8.1 Hz, 2H), 7.97 (d, J=8.4 Hz, 2H), 7.90 (s, 2H), 7.23 (t,J=7.0 Hz, 2H), 7.62 (t, J=7.7 Hz, 2H), 6.88 (d, J=8.8 Hz, 2H), 3.45 (m,8H), 2.99 (t, J=6.0 Hz, 4H), 2.10 (m, 4H), 1.74 (m, 4H), 1.42 (m, 8H),0.97 (t, J=6.6 Hz, 6H). UV-vis spectrum: λ_(max)=767 nm(dichloromethane), Fluorometry: λ_(max)=830 nm (dichloromethane).

Compound 25

Synthesis of Compound 25 was performed according to the followingscheme:

Compound 25 was prepared from Intermediate C by reaction withphenanthrenequinone, similar to the procedure described for Compound 24.Column chromatography in DCM/hexane (1:1) gave pure product of Compound25. 1H NMR (400 MHz, CDCl₃): δ 9.03 (d, J=8.1 Hz, 2H), 8.44 (d, J=8.1Hz, 2H), 8.07 (d, J=8.8 Hz, 4H), 7.76 (t, J=7.0 Hz, 2H), 7.64 (t, J=7.4Hz, 2H), 7.28-740 (m, 20H), 7.06-7.14 (m, 4H), 3.45 (m, 8H), 2.99 (t,J=6.0 Hz, 4H), 2.10 (m, 4H), 1.74 (m, 4H), 1.42 (m, 8H), 0.97 (t, J=6.6Hz, 6H). (UV-vis spectrum: λ_(max)=665 nm (dichloromethane),Fluorometry: λ_(max)=810 nm (dichloromethane).

Compound 26

Synthesis of Compound 26 was performed according to the followingscheme:

Compound 26 was prepared from Intermediate E using the same procedure asdescribed for Compound 25. ¹H NMR (400 MHz, CDCl₃): δ 9.09 (d, J=7.7 Hz,2H), 8.46 (d, J=8.1 Hz, 2H), 8.22 (d, J=8.8 Hz, 4H), 7.74 (t, J=7.0 Hz,2H), 7.64 (t, J=7.4 Hz, 2H), 7.33-7.38 (m, 20H), 7.07-7.12 (m, 4H), 4.76(d, J=7.3 Hz, 2H), 2.71 (m, 1H), 1.06 (d, J=6.6 Hz, 6H). UV-visspectrum: λ_(max)=589 nm (dichloromethane), Fluorometry: λ_(max)=716 nm(dichloromethane).

Compound 27

Synthesis of Compound 27 was performed according to the followingscheme:

Compound 27 was prepared from Intermediate E using the same procedure asdescribed for Compound 24, except6,6-dihydrocyclopentaacenaphthylene-1,2-dione is used as the reagent. ¹HNMR (400 MHz, CDCl₃): δ 8.23 (d, J=7.0 Hz, 2H), 8.13 (d, J=8.8 Hz, 4H),7.59 (d, J=7.3 Hz, 2H), 7.30-7.35 (m, 20H), 7.06-7.10 (m, 4H), 4.70 (d,J=7.3 Hz, 2H), 3.62 (s, 4H), 2.67 (m, 1H), 1.04 (d, J=7.0, 6H). UV-visspectrum: λ_(max)=517 nm (dichloromethane), Fluorometry: λ_(max)=640 nm(dichloromethane).

Compound 28

Synthesis of Compound 28 was performed according to the followingscheme:

Compound 28 was prepared from Intermediate C using the same procedure asdescribed for Compound 24, except6,6-dihydrocyclopentaacenaphthylene-1,2-dione is used as the reagent. ¹HNMR (400 MHz, CDCl₃): δ 8.25 (d, J=7.0 Hz, 2H), 7.96 (d, J=8.4 Hz, 4H),7.62 (d, 7.3 Hz, 2H), 7.30-7.40 (m, 20H), 7.06-7.10 (m, 4H), 3.63 (s,4H). UV-vis spectrum: λ_(max)=592 nm (dichloromethane), Fluorometry:λ_(max)=736 nm (dichloromethane).

Compound 29

Synthesis of Compound 29 was performed according to the followingscheme:

Compound 29 was prepared from Intermediate E and acenaphthenequinone ina mixture of acetic acid and DCM (1:1) which was stirred at roomtemperature for one hour. Column chromatography in hexane/ethyl acetate(4:1) provided Compound 29. ¹H NMR (400 MHz, CDCl₃): δ 8.29 (d, J=7.0Hz, 2H), 8.11 (d, J=8.4 Hz, 4H), 8.06 (d, J=8.4 Hz, 2H), 7.80 (t, J=8.0Hz, 2H), 7.30-7.35 (m, 20H), 7.08 (t, J=6.5 Hz, 4H).), 4.70 (d, J=7.0Hz, 2H), 2.66 (m, 1H), 1.04 (d, J=7.0 Hz, 6H). UV-vis spectrum:λ_(max)=525 nm (dichloromethane), Fluorometry: λ_(max)=660 nm(dichloromethane).

Compound 30

Synthesis of Compound 30 was performed according to the followingscheme:

Compound 30 was prepared from Intermediate C and acenaphthenequinone ina mixture of acetic acid and DCM (1:1) which was stirred at roomtemperature for one hour. Column chromatography in hexane/ethyl acetate(4:1) provided Compound 30. The reaction was monitored by TLC. ¹H NMR(400 MHz, CDCl₃): δ 8.31 (d, J=7.0 Hz, 2H), 8.11 (d, J=8.4 Hz, 2H), 7.96(d, J=8.4 Hz, 4H), 7.82 (t, J=8.0 Hz, 2H), 7.30-7.35 (m, 20H), 7.10 (m,4H). UV-vis spectrum: λ_(max)=598 nm (dichloromethane), Fluorometry:λ_(max)=756 nm (dichloromethane).

Intermediate B-5

Synthesis of Intermediate B-5 was performed according to the followingscheme:

Intermediate B-5 was prepared similarly to the procedure used forIntermediate B.

Intermediate E-5

Synthesis of Intermediate E-5 was performed according to the followingscheme:

Intermediate E-5 was prepared similarly to the procedure used forIntermediate E.

Compound 31

Synthesis of Compound 31 was performed according to the followingscheme:

Compound 31 was prepared from Intermediate E-5 and acenaphthenequinonein a mixture of acetic acid and DCM (1:1) which was stirred at roomtemperature for one hour. Column chromatography in hexane/ethyl acetate(4:1) provided Compound 31. ¹H NMR (400 MHz, CDCl₃): δ 8.31 (d, J=7.0Hz, 2H), 8.23 (d, J=8.4 Hz, 4H), 8.07 (d, J=8.0 Hz, 2H), 7.86 (d, J=8.4Hz, 4H), 7.80 (t, J=8.0 Hz, 2H), 7.67 (t, J=8.8 Hz, 4H), 7.30 (m, 8H),7.20 (m, 12H), 7.06 (t, J=7.3 Hz, 4H). UV-vis spectrum: λ_(max)=471 nm(dichloromethane), Fluorometry: λ_(max)=623 nm (dichloromethane).

Compound 32

Synthesis of Compound 32 was performed according to the followingscheme:

Compound 32 was prepared by reaction of Intermediate E-5 with3,4-hexanedione for one hour in DCM:AcOH (1:1) at room temperature. ¹HNMR (400 MHz, CDCl₃): δ 8.18 (d, J=8.4 Hz, 4H), 87.76 (d, J=7.0 Hz, 4H),7.60 (d, J=7.7 Hz, 4H), 7.25 (m, 6H), 7.16 (m, 14H), 4.03 (m, 4H).UV-vis spectrum: λ_(max)=446 nm (dichloromethane), Fluorometry:λ_(max)=545 nm (dichloromethane).

Compound 33

Synthesis of Compound 33 was performed according to the followingscheme:

Compound 33 was prepared by reaction of Intermediate E-5 withaceanthrenequinone for one hour in DCM:AcOH (1:1) at room temperature.¹H NMR (400 MHz, CDCl₃): δ 8.66 (s, 1H), 8.38 (d, J=8.3 Hz, 2H), 8.34(d, J=6.6 Hz, 1H), 8.26 (d, J=8.0 Hz, 2H), 8.20 (d, J=8.0 Hz, 2H), 7.92(d, J=8.4 Hz, 2H), 7.87 (d, J=8.4 Hz, 2H), 7.28-7.30 (m, 8H), 7.18-7.22(m, 20H), 7.05-7.08 (m, 4H). UV-vis spectrum: λ_(max)=476 nm(dichloromethane), Fluorometry: λ_(max)=623 nm (dichloromethane).

Compound 34

Synthesis of Compound 34 was performed according to the followingscheme:

Compound 34 was prepared by reaction of Intermediate E withaceanthrenequinone for one hour in DCM:AcOH (1:1) at room temperature.¹H NMR (400 MHz, CDCl₃): δ 9.45 (m, 1H), 8.65 (s, 1H), 8.32 (d, J=6.6Hz, 1H), 8.14-8.25 (3 doublets, 6H), 7.62 (m, 2H), 7.28-7.42 (m, 20H),7.08-7.13 (m, 4H). UV-vis spectrum: λ_(max)=524 nm (dichloromethane),Fluorometry: λ_(max)=658 nm (dichloromethane).

Compounds 35 and 36

Synthesis of Compound 35 and Compound 36 was performed according to thefollowing scheme:

Compound 35 and Compound 36 were prepared from Compound 26 by reactionwith 4-tert-butylbenzoylchloride (8 eq) by refluxing overnight in DCM inthe presence of anhydrous zinc chloride (8 eq).

¹H NMR for Compound 35 (first isomer isolated, eluted with DCM,monosubstituted (400 MHz, CDCl₃): δ 9.09 (t, J=8.4 Hz, 2H), 8.47 (d,J=8.1 Hz, 2H), 8.28 (d, J=8.4 Hz, 2H), 8.23 (d, J=8.4 Hz, 2H), 7.65-7.81(m, 10H), 7.49 (t, J=8.4 Hz, 6H), 7.28-7.42 (m, 12H), 7.08-7.13 (m, 3H).UV-vis spectrum: λ_(max)=581 nm (dichloromethane), Fluorometry:λ_(max)=669 nm (dichloromethane).

¹H NMR for Compound 36 (second isomer isolated, eluted with DCM plus 2%MeOH, bis-substituted) (400 MHz, CDCl₃): δ 9.08 (d, J=8.0 Hz, 2H), 8.48(d, J=8.1 Hz, 2H), 8.28 (d, J=8.4 Hz, 4H), 7.80 (d, J=8.8 Hz, 4H), 7.77(d, J=8.0 Hz, 4H), 7.66 (t, J=7.3 Hz, 2H), 7.49 (d, J=8.1 Hz, 4H), 7.48(d, J=8.0 Hz, 4H), 7.41 (m, 8H), 7.29 (d, J=8.8 Hz, 4H), 7.22 (m, 2H).UV-vis spectrum: λ_(max)=570 nm (dichloromethane), Fluorometry:λ_(max)=693 nm (dichloromethane).

Compounds 37 and 38

Synthesis of Compound 37 and Compound 38 was performed according to thefollowing scheme:

Compound 37 and Compound 38 were prepared from Compound 1 by reactionwith 4-tert-butylbenzoylchloride (8 eq) by refluxing overnight in DCM inthe presence of anhydrous zinc chloride (8 eq). Two isomers wereisolated.

¹H NMR of Compound 37 (this was the first one isolated, less polar) ¹HNMR (400 MHz, CDCl₃): δ 8.13 (d, J=8.4 Hz, 2H), 8.07 (d, J=8.0 Hz, 2H),7.75 (d, J=8.4 Hz, 4H), 7.48 (d, J=8.0 Hz, 2H), 7.18-7.37 (m, 19H), 7.05(m, 2H), 4.68 (d, J=7.5 Hz, 2H), 3.01 (q, J=7.3 Hz, 4H), 2.65 (m, 1H),1.39 (t, J=7.3 Hz, 6H), 1.35 (s, 9H), 1.02 (d, J=6.6 Hz, 6H). UV-visspectrum: λ_(max)=475 nm (dichloromethane), Fluorometry: λ_(max)=614 nm(dichloromethane).

Compound 38 was the second isomer (bis-substituted) isolated, morepolar. ¹H NMR (400 MHz, CDCl₃): δ 8.13 (d, J=8.4 Hz, 2H), 7.75 (d, J=8.8Hz, 4H), 7.48 (d, J=8.4 Hz, 2H), 7.26-7.40 (m, 24H), 7.20 (d, J=8.4 Hz,2H), 4.69 (d, J=7.3 Hz, 2H), 3.02 (q, J=7.0 Hz, 4H), 2.66 (m, 1H), 1.39(t, 7.3 Hz, 6H), 1.36 (s, 18H), 1.03 (d, J=7.0 Hz, 6H). UV-vis spectrum:λ_(max)=474 nm (dichloromethane), Fluorometry: λ_(max)=606 nm(dichloromethane).

Compound 39

Synthesis of Compound 39 was performed according to the followingscheme:

Compound 39 was obtained in two steps. First, Intermediate E was reactedwith nitrozobenzene in acetic acid, and protected from air (nitrogen)for three days. The reaction was monitored by TLC and LCMS. Afterwork-up, the solution was heated at reflux in a mixture of pyridine andTHF (1:1) in the presence of copper (II) acetate for two hours. Work-upwith water, extraction with DCM, drying, and evaporation of the solventgave crude product as a purple solid. It was purified by columnchromatography with DCM/hexane (1:1) to obtain Compound 39. ¹H NMR (400MHz, CDCl₃): δ 8.56 (d, 7.7 Hz, 2H), 7.58 (t, J=7.7 Hz, 2H), 7.48-7.52(m, 2H), 7.00-7.40 (two broadened multiplets, 27H), 14.67 (bs, 2H), 2.70(m, 1H), 1.06 (d, J=7.0, 6H). UV-vis spectrum: λ_(max)=559 nm(dichloromethane), Fluorometry: λ_(max)=671 nm (dichloromethane).

Compound 40

Synthesis of Compound 40 was performed according to the followingscheme:

Compound 40 was prepared from Compound 2 in three steps. First, Compound2 was reacted with 4-1-fluoro4-nitrobenzene to give the nitro compoundas blue solid. ¹H NMR (400 MHz, CDCl₃): δ 8.75 (d, 9.2 Hz, 2H), 8.68 (d,8.8 Hz, 4H), 7.24-7.34 (m, 20H), 7.09 (t, J=7.3 Hz, 4H), 4.67 (d, J=7.3Hz, 2H), 2.69 (m, 1H), 1.06 (d, J=6.6 Hz, 6H).

The nitro compound was then reduced by hydrogenation at 50 psi for 20minutes in a mixture of THF and MeOH, and then filtered trough Cellite,and the solvent was removed to give the amino compound as a purplesolid. ¹H NMR (400 MHz, CDCl₃): δ 8.73 (d, 8.8 Hz, 4H), 8.35 (d, 8.8 Hz,2H), 7.22-7.32 (m, 20H), 7.07 (t, J=7.3 Hz, 4H), 6.80 (d, J=8.8 Hz, 2H),4.66 (d, J=7.3 Hz, 2H), 4.0 (bs, 2H), 2.69 (m, 1H), 1.05 (d, J=7.0 Hz,6H).

The amino compound was then heated at 110° C. for 20 hours with glutaricanhydride, the temperature was lowered to 80° C. and after addition ofacetyl chloride, the solution was heated for one hour. Work-up withwater, extraction with ethyl acetate, evaporation of the solvent, andcolumn chromatography (DCM/hexane—3:2) yielded pure Compound 40 as apurple solid. ¹H NMR (400 MHz, CDCl₃): 8.70 (bs, 2H), 8.65 (d, J=8.8 Hz,2H), 7.20-7.33 (m, 24H), 7.07 (t, J=7.0 Hz, 4H), 4.67 (d, J=7.3 Hz, 2H),2.7 (s, 4H), 1.24 (s, 6H), 1.05 (d, J=6.6 Hz, 6H). UV-vis spectrum:λ_(max)=566 nm (dichloromethane), Fluorometry: λ_(max)=678 nm(dichloromethane).

Compound 41

Synthesis of Compound 41 was performed according to the followingscheme:

Step 1: In a three necked reaction flask equipped with argon inlet andmagnetic stirring bar, was placed dioxane (200 mL), Intermediate B (25.4g, 45 mmol), and argon was bubbled trough for approximately 10 minutesbefore Bis(triphenylphosphine)palladium(II) chloride (5% molar perIntermediate B, 1.60 g, 2.25 mmol) was added. The mixture was stirredunder argon for 10 minutes before Intermediate D (8.6 g, 20 mmol) wasadded in one portion. The reaction mixture was then refluxed for 4-6hours. The reaction was monitored by LCMS and TLC. Cooled and pouredinto MeOH (500 mL) while stirred. Dark orange color solid soon wasformed which was separated by filtration, washed with more MeOH, anddried to give4,4′-(2-isobutyl-5,6-dinitro-2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(N,N-diphenylaniline)(13.3 g, of purity by LCMS approx 90%).

Step 2:4,4′-(2-isobutyl-5,6-dinitro-2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(N,N-diphenylaniline)from above, crude as it was (calculated for 15.9 mmol) and iron powder(8.7 g, 160 mmol) was heated and stirred in a mixture of glacial aceticacid (50 mL), dioxane (100 mL—for solubility), and 5 ml of water (toprevent formation of side product, imidazole) at 130° C. for 2 hours.The reaction was monitored by LCMS and TLC. Cooled and poured into 500ml of ice cold water and stirred with magnetic bar retriever (to removeunreacted iron powder together with magnetic stirrer which was alsocovered with iron particles). Filtration and washing with water followedby MeOH afforded 14.9 g of crude product as olive color solid afterdrying in vacuum oven (purity by LCMS 82%). Fast column chromatography(DCM, silica gel) gave 8.2 g of pure Intermediate E,(4,7-bis(4-(diphenylamino)phenyl)-2-isobutyl-2H-benzo[d][1,2,3]triazole-5,6-diamine)¹H NMR (400 MHz, CDCl₃): δ 7.51 (δ, J=8.4 Hz, 4H), 7.28 (m, 12H), 7.19(m, 8H), 7.05 (t, J=7.4 Hz, 4H), 4.37 (d, J=7.7 Hz, 2H), 2.45 (m, 1H,i-Bu), 0.91 (d, J=7.0 Hz, 6H, i-Bu).

To obtain Compound 41, Intermediate E (8.2, 11.7 mmol) was dissolved in120 mL of THF and 30 mL of acetic acid and cooled in ice/water bath. Asolution of NaNO₂ (24 mmol, 1.65 g) in 20 mL of water was then addeddropwise. Soon the color of the reaction mixture turned to deep orange.The reaction mixture was left to stir for one hour at room temperature.The solution was then poured into 400 mL of ice cold water, whichproduced an orange-brownish solid which was separated by filtration,washed, dried, and purified by column chromatography (silicagel-DCM/hexane—3:2) to give4,4′-(6-isobutyl-1,6-dihydrobenzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-4,8-diyl)bis(N,N-diphenylaniline)as orange solid (4.95, 58%). ¹H NMR (400 MHz, CDCl₃): δ 8.5 (bs, 1H),7.9 (bs, 1H), 7.2-7.3 (m, 24H), 7.08 (t, J=7.3 Hz, 4H), 4.65 (d, J=7.4Hz, 2H), 2.64 (m, 1H), 1.01 (d, J=6.5 Hz, 6H).

The adamantane 4-methylbenzenesulfonate was synthesized by reactingadamantyl alcohol (20.5 g, 123 mmol) with p-toluenesulfonic chloride(23.6 g, 123 mmol) in 75 mL of regular DCM, in the presence of 25 mL oftriethylamine for 48 hours at room temperature. More DCM was added (100mL) and the organic layer was washed with water (3×100 mL). Drying,(MgSO4), and evaporation of the solvent gave 34.5 g of tea color oilwhich under trituration with hexane afforded white solid adamantane4-methylbenzenesulfonate (30.5 g, 76%).

Then,4,4′-(6-isobutyl-1,6-dihydrobenzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-4,8-diyl)bis(N,N-diphenylaniline(4.9 g, 7 mmol) was dissolved in NMP (50 mL). Potassium carbonate (4.2g, 30 mmol) was added, followed by adamantane 4-methylbenzenesulfonate(2.7 g, 8.4 mmol) and reaction mixture was heated at 175° C. for 4-5hours. The reaction was monitored by LCMS and TLC. Two isomers wereformed, the major one, was the desired product (Bt-2 isomer) and is oflower polarity. With longer time and higher temperature, more of theside product of higher polarity (Bt-1 isomer) is formed. After almostall starting material was consumed, the reaction mixture was cooled,poured into ice-cold water (400 mL), and left to stir, allowingformation of fine precipitate. The solid was filtered, washed withwater, and dried to give 6.9 g of crude dark purple product. Columnchromatography (silica gel, DCM/Hexane-3:2) provided Compound 41,(2-((3r,5r,7r)-adamantan-1-ylmethyl)-4,8-bis(4-(diphenylamino)phenyl)-6-isobutyl-2H-benzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-6-ium-5-ide)(2.42 g, 40%). ¹H NMR (400 MHz, toluene-d₃): δ 9.15 (d, J=8.7 Hz, 4H),7.41 (d, J=8.8 Hz, 4H), 7.13, m, 8H, overlapped with toluene), 7.02 (8H,overlapped with toluene), 6.84 (t, J=7.3 Hz, 4H), 4.25 (bs, 4H, 2×CH₂),2.40 (m, 1H), 1.72 (bs, 3H), 1.51 (bs, 6H), 1.46 (bs, 3H), 1.36 (bs,3H), 0.70 (d, J=7.0 Hz, 6H). UV-vis spectrum: λ_(max)=520 nm(dichloromethane), Fluorometry: λ_(max)=610 nm (dichloromethane).

Compound 42

Synthesis of Compound 42 was performed according to the followingprocedures:

Compound 42 was prepared from Compound 6 by alkylation with2-butoxyethyl-tosylate for one hour at 100° C. The mixture was pouredinto water and the solid obtained was separated, washed with water,followed by MeOH, dried, and purified by column chromatography(DCM/hexane) to give product as red solid, Compound 42. ¹H NMR (400 MHz,CDCl₃): δ 8.59 (d, J=8.8 Hz, 4H), 7.38 (t, J=7.7 Hz, 8H), 7.12-7.16 (m,16H), 5.07 (t, J=5.1 Hz, 2H), 4.73 (s, 2H), 4.11 (t, J=5.1 Hz, 2H), 3.40(m, 2H), 1.36 (m, 2H), 1.10 (m, 2H), 1.06 (s, 9H), 0.65 (t, J=7.3 Hz,3H). UV-vis spectrum: λ_(max)=522 nm (dichloromethane), Fluorometry:λ_(max)=616 nm (dichloromethane).

Compound 43

Synthesis of Compound 43 was performed according to the followingprocedures:

Compound 43 was prepared similar to the procedure described for Compound42, except neopentyl tosylate is used instead. ¹H NMR (400 MHz,DMSO-d₆): δ 8.61 (d, J=8.8 Hz, 4H), 8.16 (s, 4H), 7.33 (m, 8H),7.08-7.35 (m, 14H), 4.67 (s, 4H), 1.06 (s, 18H). UV-vis spectrum:λ_(max)=522 nm (dichloromethane), Fluorometry: λ_(max)=613 nm(dichloromethane).

Compound 44

Synthesis of Compound 44 was performed according to the followingprocedures:

Compound 44 was prepared similar to the procedure described for Compound42, except adamantyl tosylate is used instead. ¹H NMR (400 MHz,toluene-t₃): δ 9.18 (d, J=8.8 Hz, 4H), 7.42 (d, J=8.8 Hz, 4H), 7.08-7.15(m, 8H, overlapped with toluene), 7.00-7.04 (m, 8H, overlapped withtoluene), 6.84 (t, J=7.3 Hz, 4H), 4.28 (s, 2H), 4.24 (s, 2H), 1.72 (bs,3H), 1.50 bs, 2H), 1.46 (bs, 2H), 1.38 (bs, 2H), 1.35 (bs, 2H), 0.88 (s,9H). UV-vis spectrum: λ_(max)=521 nm (dichloromethane), Fluorometry:λ_(max)=611 nm (dichloromethane).

Compound 45

Synthesis of Compound 45 was performed according to the followingprocedures:

Compound 45 was prepared by alkylation of Compound 7 with1,4-dibromobutane followed by reaction with 4-cyanophenol under standardconditions. ¹H NMR (400 MHz, toluene-d₃): δ 9.10 (d, J=9.2 Hz, 4H), 7.41(d, 8.8 Hz, 4H), 7.14 (d, J=7.7 Hz, 8H), 7.05 (d, J=7.3 Hz, 8H), twoprotons overlapped with toluene, 6.87 (t, J=7.3 Hz, 4H), 6.25 (d, J=8.8Hz, 2H), 4.40 (t, J=7.1 Hz, 2H), 4.29 (s, 2H), 3.14 (t, J=6.2 Hz, 2H),1.35 (m, 4H), 0.88 (s, 9H). UV-vis spectrum: λ_(max)=519 nm(dichloromethane), Fluorometry: λ_(max)=616 nm (dichloromethane).

Compound 46

Synthesis of Compound 46 was performed according to the followingprocedures:

Compound 46 was prepared similar to the procedure described for Compound45, except alkylation was performed with 1,5-dibromopentane. UV-visspectrum: λ_(max)=520 nm (dichloromethane), Fluorometry: λ_(max)=613 nm(dichloromethane).

Compound 47

Synthesis of Compound 47 was performed according to the followingprocedures:

Compound 47 was prepared from Compound 46, and further reacted with4-hydroxyacetophenone at 130° C. for five hours (monitored by LCMS andTLC). Column chromatography (DCM/hexane-3:2) provided pure productCompound 47. ¹H NMR (400 MHz, CDCl₃): δ 8.62 (d, J=8.8 Hz, 4H), 7.85 (d,J=8.8 Hz, 2H), 7.18-7.24 (m, 20H), 7.06 (t, J=7.3 Hz, 4H), 6.84 (d,J=8.8 Hz, 2H), 4.90 (t, J=7.3 Hz, 2H), 4.66 (s, 2H), 4.00 (t, J=4.8 Hz,2H), 2.5 (s, 3H), 2.32 (m, 2H), 1.90 (m, 2H), 1.63 (m, 2H), 1.13 (S,9H). (UV-vis spectrum: λ_(max)=520 nm (dichloromethane), Fluorometry:λ_(max)=614 nm (dichloromethane).

Compound 48

Synthesis of Compound 48 was performed according to the followingscheme:

Compound 48 was prepared according to the scheme above, with twochromophores connected. One of the chromophores, the smaller one, servesas internal UV protector, to improve the stability of the originalchromophore. Two isomers have been isolated (Bt(2)-Bt(2) of lowerpolarity and Bt(1)-Bt(2) of higher polarity. One, predominant isreported. ¹H NMR (400 MHz, toluene-d₃) for Compound 48 (Bt-2-Bt-2),isomer: δ 9.09 (d, J=9.1 Hz, 4H), 8.22 (J=8.8 Hz, 4H), 7.59 (s, 2H),7.47 (d, J=8.4 Hz, 4H), 7.40 (d, J=9.1 Hz, 4H), 7.12 (m, 8H) and 7.02(m, 8H) overlapped with toluene, 6.84 (t, J=7.3 Hz, 4H), 4.25 (m, 4H),1.70 (m, 4H), 1.30 (s, 18H), 0.88 (s, 9H). UV-vis spectrum: λ_(max)=521nm (dichloromethane), Fluorometry: λ_(max)=613 nm (dichloromethane).

Compound 49

Synthesis of Compound 49 was performed according to the followingscheme:

Compound 49 was prepared according to the scheme above, with twochromophores connected. One of the chromophores, the smaller one, servesas internal UV protector, to improve the stability of the originalchromophore. Two isomers have been isolated (Bt(2)-Bt(2) of lowerpolarity and Bt(1)-Bt(2) of higher polarity. One, predominant isreported. ¹H NMR (400 MHz, CDCl₃) for Compound 49 (Bt-2-Bt-2), isomer: δ8.59 (d, J=8.8 Hz, 4H), 7.96 (d, J=8.8 Hz, 4H), 7.52 (s, 2H), 7.19-7.27,m, 30H), 7.04 (t, J=7.0 Hz, 4H), 7.0 (d, J=8.8 Hz, 4H), 4.83 (t, J=7.2Hz, 2H), 4.75 (t, J=7.2 Hz, 2H), 4.65 (d, J=7.3 Hz, 2H), 3.75 (d, J=6.6Hz, 4H), 1.05 (m, 1H), 2.08-2.23 (m, 8H), 1.02 (2 doublets, 18H).

Compound 50

Synthesis of Compound 50 was performed according to the followingscheme:

Compound 50 was prepared according to the scheme above, with twochromophores connected. One of the chromophores, the smaller one, servesas internal UV protector, to improve the stability of the originalchromophore. Two isomers have been isolated (Bt(2)-Bt(2) of lowerpolarity and Bt(1)-Bt(2) of higher polarity. One, predominant isreported. ¹H NMR (400 MHz, CDCl₃) for Compound 50 (Bt-2-Bt-2), isomer: δ8.59 (d, J=8.8 Hz, 4H), 7.79 (m, 2H), 7.67 (m, 2H), 7.15-7.34 (m, 20H),7.05 (t, J=7.3 Hz, 4H), 4.83 (t, J=7.0 Hz, 2H), 4.65 (d, J=7.3 Hz, 2H),3.66 (t, J=7.0 Hz, 2H), 2.67 (m, 1H), 2.22 (m, 2H), 1.68 (m, 2H),1.4-1.5 (m, 4H), 1.03 (d, J=6.6 Hz, 6H).

Compound 51

Synthesis of Compound 51 was performed according to the followingscheme:

Compound 51 was prepared according to the scheme above, using standardalkylation procedure.

Compound 52

Synthesis of Compound 52 was performed according to the followingscheme:

Compound 52 was obtained by acylation of Compound 51. ¹H NMR (400 MHz,CDCl₃)): δ 8.64 (d, J=8.8 Hz, 6H), 7.84 (d, J=8.8 Hz, 6H), 7.11-7.35 (m,40H), 4.99 (bs, 4H), 4.66 (bs, 4H), 3.27 (m, 4H), 2.39 (bs, 4H),1.72-1.80 (m, 8H), 1.45-1.62 (m, 8H), 1.21-1.28 (m, 16H), 1.13 (s, 18H),0.86 (m, 24H-8 triplets overlapped)

Compound 53

Synthesis of Compound 53 was performed according to the followingscheme:

Compound 53 was obtained by alkylation of Compound 51 (1194-26B). ¹H NMR(400 MHz, CDCl₃)): δ 9.08 (d, J=8.8 Hz, 8H), 7.48 (8.8 Hz, 8H), 7.21 (d,J=8.4 Hz, 16H), 7.11 (m, 8H), 6.98 (m, 8H), 4.29 bs, 8H), 1.51-1.55 (m,8H), 1.20 (s, 66H), 1.45-0.80 (multiplets, 68H).

Intermediate B-6

Synthesis of Intermediate B-6 was performed according to the followingscheme:

Intermediate B-6 was prepared following a similar procedure to thatdescribed for Intermediate B.

Intermediate C-6

Synthesis of Intermediate C-6 was performed according to the followingscheme:

Intermediate C-6 was prepared following a similar procedure to thatdescribed for Intermediate C, except that Intermediate B-6 was usedinstead of Intermediate B.

Compound 54

Synthesis of Compound 54 was performed according to the followingscheme:

Compound 54 was prepared following the same procedure as for Compound 4except that Intermediate C-6 was used instead of Intermediate C. ¹H NMR(400 MHz, CHCl₃): δ 8.47 bs, 2H), 7.84 (bs, 2H), 6.88 (b, 4H), 3.37 (m,8H), 1.64-1.74 (m, 8H), 1.31-1.41 (m, 16H), 0.94 (t, J=7.0 Hz, 12H).UV-vis spectrum: λ_(max)=602 nm (dichloromethane), Fluorometry:λ_(max)=742 nm (dichloromethane).

Compound 55

Synthesis of Compound 55 was performed according to the followingprocedures:

Compound 55 was prepared from Compound 54 by alkylation withmethylmethanesulfonate in the presence of potassium carbonate in DMF at65° C. for 3 hours. ¹H NMR (400 MHz, CDCl₃): δ 8.31 (d, J=9.2 Hz, 4H),6.85 (d, J=9.2 Hz, 4H), 3.36 (m, 8H), 2.15 (s, 3H), 1.68 (m, 8H), 1.53(m, 8H), 1.36 (m, 8H), 0.93 (t, J=6.6 Hz, 12H). UV-vis spectrum:λ_(max)=645 nm (dichloromethane), Fluorometry: 798 nm (dichloromethane).

Compound 56

Synthesis of Compound 56 was performed according to the followingprocedures:

Compound 56 was prepared from Compound 54 by alkylation with tosylate of2-ethylhexanol (prepared according to general procedure) in the presenceof potassium carbonate (4 eq) in DMF at 65° C. for 3 hours. ¹H NMR—noNMR, no sample). UV-vis spectrum: λ_(max)=659 nm (dichloromethane),Fluorometry: 812 nm (dichloromethane). Small sample, characterized onlyby LCMS.

Compound 57

Synthesis of Compound 57 was performed according to the followingscheme:

Compound 57 was prepared from Intermediate C-6 by reaction with benzoylchloride (1.1 eq) in refluxing toluene for one hour. Work-up with coldsodium bicarbonate and water, evaporation of the solvent followed bycolumn chromatography (DCM/hexane-3:2 gave pure product as purple oil,Compound 57. ¹H NMR (400 MHz, CHCl₃): δ 9.42 (s, 1H), 8.33 (d, J=8.4 Hz,2H), 8.14 (m, 2H), 7.78 (d, J=8.1 Hz, 2H), 7.52 (m, 3H), 6.86 (m, 2H),3.37 (t, J=7.3 Hz, 8H), 1.57-1.72 (m, 8H), 1.25-1.44 (m, 16H), 0.91 (t,J=7.3 Hz, 12H). UV-vis spectrum: λ_(max)=537 nm (dichloromethane),Fluorometry: λ_(max)=675 nm (dichloromethane).

Compound 58

Synthesis of Compound 58 was performed according to the followingprocedures:

Compound 58 was prepared by alkylation of Compound 57 with tosylate ofisobutyl alcohol in DMF (under standard condition), at 90° C.,overnight. The structure was confirmed by LCMS, very small sampleobtained. UV-vis spectrum: λ_(max)=516 nm (dichloromethane),Fluorometry: λ_(max)=668 nm (dichloromethane).

Compound 59

Synthesis of Compound 59 was performed according to the followingprocedures:

Compound 59 was prepared from Compound 4 by reaction with4-chloropyridine (2 eq) in quinoline at 190° C. overnight. Work-up withsodium carbonate solution and DCM, then the organic layer was dried,rotavaped, and diluted with methanol until the precipitate was formed.Chromatographed with DCM-2.5% ethyl acetate. Pure product was obtainedas a bluish-green solid. ¹H NMR (400 MHz, CDCl₃): δ 8.87 (d, J=5.9 Hz,2H), 8.45 (m, 6H, two doublets overlapped), 7.2-7.4 (m, 20H), 7.11 (t,J=7.4 Hz, 4H). UV-vis spectrum: λ_(max)=684 nm (dichloromethane),Fluorometry: λ_(max)=820 nm (dichloromethane).

Compound 60

Synthesis of Compound 60 was performed according to the followingprocedures:

Compound 60 was prepared similarly to Compound 59 except4-fluoroethylbenzoate was used instead (4 eq). The reaction time was 4days. Cooling and diluting with methanol afforded crude product whichwas purified by column chromatography (hexane-ethyl acetate, 4:1). ¹HNMR (400 MHz, CDCl₃): δ 8.36 (d, J=8.8 Hz, 4H), 7.22-7.40 (m, 22H), 7.08(t, J=7.0 Hz, 6H), 4.95 (q, J=7.3 Hz, 2H), 1.83 (t, J=7.3 Hz, 3H).UV-vis spectrum: λ_(max)=607 nm (dichloromethane), Fluorometry:λ_(max)=751 nm (dichloromethane).

Compound 61

Synthesis of Compound 61 was performed according to the followingprocedures:

Compound 61 was prepared from Compound 59 by acylation with valerylchloride in the presence of zinc chloride in anhydrous DCM at reflux forfour hours. The reaction mixture was cooled, poured into ice-cold sodiumbicarbonate and stirred for 30 minutes. The organic layer was washedwith sodium bicarbonate, followed by water, dried, and the solvent wasevaporated. Column chromatography (DCM-ethyl acetate 2.5%-20%) affordedpure product. ¹H NMR (400 MHz, CDCl₃): δ 8.92 (m, 2H), 8.56 (d, J=8.8Hz, 4H), 8.48 (d, J=6.2 Hz, 2H), 7.94 (d, J=8.8 Hz, 4H), 7.41 (d, J=8.4Hz, 4H), 7.28 (m, 14H), 2.95 (t, J=7.7 Hz, 8H), 1.74 (m, 8H), 1.44 (m,8H), 0.97 (t, J=7.3 Hz, 12H). UV-vis spectrum: λ_(max)=632 nm(dichloromethane), Fluorometry: λ_(max)=794 nm (dichloromethane).

Compounds 62 and 63

Synthesis of Compound 62 and Compound 63 was performed according to thefollowing procedures:

Compounds 62 and Compound 63 were prepared from Compound 5, using aprocedure similar to that described for Compound 61. UV-vis spectrum ofCompounds 62 and 63 were the same: λ_(max)=588/586 nm (dichloromethane),Fluorometry: λ_(max)=688/682 nm (dichloromethane), respectively.

Compounds 64-69

Synthesis of Compound 64, 65, 66, 67, 68, and 69 were performedaccording according to the following procedures:

Compounds 64, 65, 66, 67, 68, and 69 were prepared according to thegeneral procedure for alkylation of benzotriazole as is described forCompound 3. Their optical properties are almost identical. Only one setof NMR data is presented below as representatives of two isomers ofbenzotriazole formed at different ratio depending on the temperature ofthe reaction. Benzotriazole-1 (as Compound 66) is predominantly formedat higher temperature and benzotriazole-2 (as Compound 67) at lowertemperature.

¹H NMR for Compound 66 isomer (400 MHz, CDCl₃): δ 8.35 (d, J=8.4 Hz,2H), 7.46 (d, J=8.4 Hz, 2H), 7.18-7.34 (m, 18H), 7.08 (m, 6H), 4.51 (t,J=7.8 Hz, 2H), 1.54 (m, 2H), 1.14 (m, 2H), 0.82 (t, J=7.3 Hz, 3H).).UV-vis spectrum: λ_(max)=536 nm (dichloromethane), Fluorometry:λ_(max)=681 nm (dichloromethane).

¹H NMR for Compound 67 isomer (400 MHz, CDCl₃): δ 8.92 8.36 (d, J=8.8Hz, 4H), 7.22-7.32 (m, 20H), 7.08 (t, J=7.3 Hz, 4H), 4.88 (t, J=7.3 Hz,2H), 2.22 (m, 2H), 1.46 (m, 2H), 1.00 (t, J=7.3 Hz, 3H). UV-visspectrum: λ_(max)=603 nm (dichloromethane), Fluorometry: λ_(max)=747 nm(dichloromethane).

Compound 68 was prepared by analogy to Compound 66. Two isomers werealso separated. ¹H NMR for Compound 68 isomer (400 MHz, CDCl₃): δ 8.35(d, J=8.8 Hz, 2H), 7.46 (d, J=8.8 Hz, 2H), 7.15-7.39 (m, 20H), 7.09 (m,4H), 4.35 (d, J=7.4 Hz, 2H), 1.73 (m, 1H), 1.14 (m, 2H), 0.69 (d, J=6.6Hz, 6H).). UV-vis spectrum: λ_(max)=529 nm (dichloromethane),Fluorometry: λ_(max)=681 nm (dichloromethane).

¹H NMR for Compound 69 isomer (400 MHz, CDCl₃): δ 8.36 (d, J=8.8 Hz,4H), 7.22-7.32 (m, 20H), 7.08 (t, J=7.3 Hz, 4H), 4.69 (d, J=7.3 Hz, 2H),2.69 (m, 1H), 1.04 (d, J=7.0 Hz, 6H). UV-vis spectrum: λ_(max)=604 nm(dichloromethane), Fluorometry: λ_(max)=750 nm (dichloromethane).

Compound 70

Synthesis of Compound 70 was performed according to the followingprocedures:

Compound 70 was prepared from Compound 69 by alkylation with2-methyl-2-hexanol (12 eq) in refluxing TFA for six hours. The reactionwas monitored by TLC, where the blue spot disappeared and dark green oflower polarity indicated product. Evaporation and column chromatography(DCM/hexane—2:3) gave pure tetraalkylated product. ¹H NMR (400 MHz,CDCl₃): δ 8.35 (d, J=8.4 Hz, 4H), 7.24 (m, 12H), 7.15 (d, J=8.4 Hz, 8H),4.68 (d, J=7.3 Hz, 2H), 2.70 (m, 1H), 1.59 (t, J=6.0 Hz, 8H), 1.29 (s,24H), 1.26 (m, 8H), 1.09 (m, 8H), 1.04 (d, 6.6 Hz, 6H), 0.86 (t, J=7.3Hz, 12H). UV-vis spectrum: λ_(max)=626 nm (dichloromethane),Fluorometry: λ_(max)=787 nm (dichloromethane).

Compounds 71 and 72

Synthesis of Compound 71 and Compound 72 were performed according to thefollowing procedures:

Compounds 71 and 72 were prepared by reaction of Compound 4 with2,6-difluorobenzylbromide (1.5 eq) in the presence of potassiumcarbonate (5 eq), in DMF, for one hour at 130° C. Two isomers wereformed. For the first time benzotriazole-2 was formed as predominant,probably due to bulkiness of the bromide used. The best way to assignwhich isomers are formed is by position of the methylene group attachedto benzotriazole. Benzotriazole-2 is downfield in comparison tobenzotriazole-1. They are easily separated due to different polarity andcolor.

Compound 71 Bt(1) isomer: (400 MHz, CDCl₃): δ 8.35 (d, J=9.1 Hz, 2H),7.38 (d, J=8.4 Hz, 2H), 7.17-7.35 (m, 21H), 7.09 (m, 4H), 6.79 (t, J=8.1Hz, 2H), 5.69 (s, 2H).). UV-vis spectrum: λ_(max)=535 nm(dichloromethane), Fluorometry: λ_(max)=684 nm (dichloromethane).

Compound 72 Bt(2) isomer: (400 MHz, CDCl₃): δ 8.36 (d, J=8.8 Hz, 4H),7.30 (t, J=8.4 Hz, 8H), 7.21-7.25 (m, 13H), 7.08 (t, J=7.3 Hz, 4H), 6.98(t, J=8.4 Hz, 2H), 6.14 (s, 2H). (UV-vis spectrum: λ_(max)=612 nm(dichloromethane), Fluorometry: λ_(max)=764 nm (dichloromethane).

Compound 73

Synthesis of Compound 73 was performed according to the followingprocedures:

Compound 73 was obtained by reacting Compound 2 with4-fluorobenzonitrile (2 eq) by heating in DMF for one hour in thepresence of potassium carbonate (5 eq). Only benzotriazole-2 isomer wasformed. (400 MHz, CDCl₃): δ 9.01 (d, J=2.2 Hz, 1H), 8.93 (dd, J=2.2 and8.8 Hz, 1H), 8.62 (d, J=8.8 Hz, 4H), 8.02 (d, J=8.8 Hz, 1H), 7.23-7.34(m, 20H), 7.10 (t, J=7.3 Hz, 4H), 4.67 (d, J=7.3 Hz, 2H), 2.69 (m, 1H),1.06 (d, J=6.6 Hz, 6H). UV-vis spectrum: λ_(max)=626 nm(dichloromethane), Fluorometry: λ_(max)=783 nm (dichloromethane).

Compound 74

Synthesis of Compound 74 was performed according to the followingprocedures:

Compound 74 was obtained from Compound 4 by alkylation with tosylate of2-butoxyethanol (2 eq) in the presence of potassium carbonate (5 eq) inDMF at 80° C. for 30 minutes. Under this condition only benzotriazole-2isomer is formed. Pouring into water afforded solid which was separatedby filtration, washed with water, followed by methanol, dried, andsubjected to column chromatography (DCM/hexane—3:2) to give pure productas dark blue solid. ¹H NMR (400 MHz, CDCl₃): δ 8.36 (d, J=8.8 Hz, 4H),7.22-7.32 (m, 20H), 7.08 (t, J=8.8 Hz, 4H), 5.05 (t, J=5.9 Hz, 2H), 4.21(t, J=5.9 Hz, 2H), 3.48 (t, J=6.6 Hz, 2H), 1.48 (m, 2H), 1.24 (m, 2H),0.77 (t, J=7.3 Hz, 3H). UV-vis spectrum: λ_(max)=606 nm(dichloromethane), Fluorometry: λ_(max)=752 nm (dichloromethane).

Compound 75

Synthesis of Compound 75 was performed according to the followingprocedures:

Compound 75 was prepared from Intermediate C by reaction with benzoylchloride in refluxing toluene for one hour. Work-up with ice coldNaHCO₃, dried, and the solvent removed, followed by columnchromatography (DCM/hexane-3:2) gave pure product as a pink solid. ¹HNMR (400 MHz, CDCl₃): δ 9.48 (s, 1H), 8.36 (d, J=8.8 Hz, 2H), 8.14 (m,2H), 7.81 (d, J=8.4 Hz, 2H), 7.54 (bs, 3H), 7.2-7.4 (m, 22H), 7.10 (m,4H). UV-vis spectrum: λ_(max)=502 nm (dichloromethane), Fluorometry:λ_(max)=637 nm (dichloromethane).

Compound 76

Synthesis of Compound 76 was performed according to the followingprocedures:

Compound 76 was prepared from Compound 2 by alkylation with tosylateprepared from isobutyl alcohol following the same procedure used forCompound 3. ¹H NMR (400 MHz, CDCl₃): δ 8.61 (d, J=8.8 Hz, 4H), 7.16-7.36(m, 20H), 7.06 (t, J=7.2 Hz, 4H), 4.66 (d, J=7.0 Hz, 4H), 2.67 (m, 2H),1.03 (d, J=6.6 Hz, 12H). UV-vis spectrum: λ_(max)=512 nm(dichloromethane), Fluorometry: λ_(max)=611 nm (dichloromethane).

Compound 77

Synthesis of Compound 77 was performed according to the followingprocedures:

Compound 77 was prepared from Intermediate E by reaction with seleniumoxide dissolved in hot water added to solution of Intermediate E in hotethanol. The reaction mixture was heated at reflux for five hours. Aftercooling, the solid was separated, washed with methanol and dried. Columnchromatography with DCM gave pure product as a dark green solid. ¹H NMR(400 MHz, CDCl₃): δ 8.25 (d, J=8.4 Hz, 4H), 7.22-7.32 (m, 20H), 7.07 (t,J=7.0 Hz, 4H), 4.63 (d, J=7.3 Hz, 2H), 2.68 (m, 1H), 1.04 (d, J=6.6 Hz,6H). UV-vis spectrum: λ_(max)=669 nm (dichloromethane), Fluorometry:λ_(max)=807 nm (dichloromethane).

Compound 78

Synthesis of Compound 78 was performed according to the followingprocedures:

Compound 78 was prepared from Intermediate C by reaction with valerylchloride (1.1 eq) in refluxing toluene, for two hours. Columnchromatography without work-up (DCM/hexane—3:2) afforded pure product aspurple solid. ¹H NMR (400 MHz, CDCl₃): δ 8.20 (bs, J=2H), 7.75 (bs, 2H),7.20-7.29 (m, 20H), 2.94 (t, J=8.0 Hz, 2H), 1.83-1.90 (m, 2H), 1.46-1.54(m, 2H), 0.98 (t, J=7.3 Hz, 3H). UV-vis spectrum: λ_(max)=480 nm(dichloromethane), Fluorometry: λ_(max)=622 nm (dichloromethane).

Compound 79

Synthesis of Compound 79 was performed according to the followingprocedures:

Compound 79 was prepared from Intermediate C and 3,4-hexanedione usingthe same procedure used for Compound 1, at room temperature in DCM inthe presence of acetic acid (it takes 15 minutes to accomplish).Evaporation of the solvent and trituration with methanol gives pureproduct as a violet solid. ¹H NMR (400 MHz, CDCl₃): δ 7.89 (d, J=8.8 Hz,4H), 7.24-7.30 (m, 20H), 7.06 (t, J=7.0 Hz, 4H), 3.01 (q, J=7.0 Hz, 4H),1.38 (t, J=7.3 Hz, 6H). UV-vis spectrum: λ_(max)=561 nm(dichloromethane), Fluorometry: λ_(max)=725 nm (dichloromethane).

Compound 80

Synthesis of Compound 80 was performed according to the followingprocedures:

Compound 80 was obtained from Compound 78 (following standard procedurefor alkylation with tosylate of isobutyl alcohol for four hours at 120°C. UV-vis spectrum: λ_(max)=472 nm (dichloromethane), Fluorometry:λ_(max)=616 nm (dichloromethane).

Compound 81

Synthesis of Compound 81 was performed according to the followingprocedures:

Compound 81 was obtained from Intermediate C with benzil in DCM in thepresence of acetic acid and stirred for one hour at room temperature.Column chromatography (DCM/hexane) provided pure product as a dark bluesolid. ¹H NMR (400 MHz, CDCl₃): δ 7.96 (d, J=8.4 Hz, 4H), 7.65 (d, J=7.3Hz, 4H), 7.25-7.34 (m, 26H), 7.09 (t, J=7.3 Hz, 4H). UV-vis spectrum:λ_(max)=609 nm (dichloromethane), Fluorometry: λ_(max)=777 nm(dichloromethane).

Intermediate B-7

Synthesis of Intermediate B-7 was performed according to the followingscheme:

Intermediate B-7 was prepared similarly to the procedure used forIntermediate B. In the first step 4-iodophenol was alkylated withtosylate of isobutyl alcohol with close to quantitative yield. The crudeproduct was used directly for the preparation of stannyl derivativeaccording to the general procedure.

Intermediate C-7

Synthesis of Intermediate C-7 was performed according to the followingscheme:

Intermediate C-7 was prepared similarly to the procedure used forIntermediate C. The crude product from Intermediate B-7 (yellowish oil)was used for the Stille coupling with Intermediate A (5 hours reflux inTHF). Work-up with water and DCM, evaporation of the solvent andtrituration with MeOH gave the nitro-derivative as a yellow solid. Itwas reduced with iron powder (10 eq) at 130° C. in acetic acid with 5%of water at 130 C for two hours. Pouring into water affordedyellowish-green solid which was dried and washed through a layer ofsilica gel to remove particles of iron (DCM/hexane, 1:1). All steps weremonitored by TLC and LCMS (purity above 80%). The crude product wascyclized to benzotriazole under standard conditions. Purification bycolumn chromatography gave a reddish-orange solid.

Compound 82

Synthesis of Compound 82 was performed according to the followingscheme:

Compound 82 was prepared using Intermediate C-7. ¹H NMR (400 MHz,CDCl₃): δ 8.39 (bs, 2H), 7.86 bs, 2H)), 7.06 (d, J=8.1 Hz, 4H), 3.81 (d,J=6.2 Hz, 4H), 2.14 (m, 2H), 1.05 (d, J=6.6 Hz, 6H). UV-vis spectrum:λ_(max)=490 nm (dichloromethane), Fluorometry: λ_(max)=603 nm(dichloromethane).

Compound 83

Synthesis of Compound 83 was performed according to the followingscheme:

Compound 83 was prepared from Intermediate C-7 by reaction with seleniumoxide in a mixture of ethanol and water (2:1) by refluxing for one hour.Evaporation of the solvent gave solid which was separated, washed withwater followed by methanol, and dried to give a pure dark green solid.¹H NMR (400 MHz, CDCl₃): δ 8.08 (d, J=8.4 Hz, 4H), 7.15 (d, J=8.4 Hz,4H)), 3.85 (d, J=6.6 Hz, 4H), 2.16 (m, 2H), 1.06 (d, J=6.6 Hz, 6H).UV-vis spectrum: λ_(max)=674 nm (dichloromethane), Fluorometry:λ_(max)=806 nm (dichloromethane).

Compound 84

Synthesis of Compound 84 was performed according to the followingscheme:

Compound 84 was prepared from Intermediate C-7 by reaction withthionylpyridine in dry pyridine, in the presence oftrimethylsilylchloride, for four hours at 80° C. Column chromatography(DCM/hexane) afforded pure product. ¹H NMR (400 MHz, CDCl₃): δ 8.16 (d,J=8.8 Hz, 4H), 7.16 (d, J=9.1 Hz, 4H), 3.85 (d, J=6.7 Hz, 4H), 2.16 (m,2H), 1.06 (d, J=6.6 Hz, 6H). UV-vis spectrum: λ_(max)=605 nm(dichloromethane), Fluorometry: λ_(max)=732 nm (dichloromethane).

Intermediate E-7

Synthesis of Intermediate E-7 was performed according to the followingscheme:

Intermediate E-7 was prepared similarly to the procedure used forIntermediate E.

Compound 85

Synthesis of Compound 85 was performed according to the followingscheme:

Compound 85 was obtained as red solid and was prepared starting fromIntermediate E-7 using the same procedure that was used for Compound 81,with benzyl (1:1 molar ratio) in DCM, at room temperature in thepresence of acetic acid. ¹H NMR (400 MHz, CDCl₃): δ 8.11 (d, J=8.4 Hz,4H), 7.63 (d, J=7.7 Hz, 4H), 7.30 (m, 6H), 7.14 (d, J=8.8 Hz, 4H), 4.70(d, J=7.3 Hz, 2H), 4.12 (m, 2H), 3.86 (d, J=6.6 Hz, 4H), 2.15 (m, 1H),1.08 (d, J=7.0 Hz, 12H), 1.03 (d, J=6.6 Hz, 6H). UV-vis spectrum:λ_(max)=477 nm (dichloromethane), Fluorometry: λ_(max)=577 nm(dichloromethane).

Compound 86

Synthesis of Compound 86 was performed according to the followingscheme:

Compound 86 was prepared similarly to Compound 85, except firstpreparing benzotriazole from Intermediate E-7, and then alkylation withtosylate of isobutyl alcohol under standard condition. ¹H NMR (400 MHz,CDCl₃): δ 8.54 (d, J=8.8 Hz, 4H), 7.11 (d, J=8.8 Hz, 4H), 4.67 (d, J=7.3Hz, 2H), 4.12 (m, 4H), 3.83 (d, J=6.6 Hz, 4H), 2.68 (m, 2H), 2.15 (m,2H), 1.05 (d, J=6.6 Hz, 12H, 1.04 (d, J=7.0 Hz, 12H). UV-vis spectrum:λ_(max)=471 nm (dichloromethane), Fluorometry: λ_(max)=537 nm(dichloromethane).

Intermediate B-8

Synthesis of Intermediate B-8 was performed according to the followingscheme:

Intermediate B-8 was prepared similarly to the procedure used forIntermediate B.

Intermediate C-8

Synthesis of Intermediate C-8 was performed according to the followingscheme:

Intermediate C-8 was prepared similarly to the procedure used forIntermediate C.

Compound 87

Synthesis of Compound 87 was performed according to the followingscheme:

Compound 86 was prepared by reaction of Intermediate C-8 with thionylaniline (0.8 mL per one mmol) in the presence of trimethylsilyl chloride(3 eq) in dry pyridine at 80° C. Work-up with water afforded crude darkgreenish-blue solid which was purified by column chromatography (DCM/5%THF) to give pure product. ¹H NMR (400 MHz, CDCl₃): δ 7.71 (s, 4H), 3.26(t, J=5.5 Hz, 8H), 2.90 (t, J=6.2 Hz, 8H), 2.04 (m, 8H). UV-visspectrum: λ_(max)=801 nm (dichloromethane), Fluorometry: λ_(max)=831 nm(dichloromethane).

Compound 88

Synthesis of Compound 88 was performed according to the followingscheme:

Compound 88 was prepared from Intermediate C-8 following the sameprocedure used for Compound 2. ¹H NMR (400 MHz, CDCl₃): δ 6.94 (s, 4H),3.18 (t, J=5.5 Hz, 8H), 2.82 (t, J=6.4 Hz, 8H), 2.00 (, 8H). (UV-visspectrum: λ_(max)=602 nm (dichloromethane), Fluorometry: λ_(max)=742 nm(dichloromethane).

Compound 89

Synthesis of Compound 89 was performed according to the followingscheme:

Compound 89 was prepared from Intermediate C-8 with 3,4-cyclohexanedionein DCM in the presence of acetic acid according to the same procedureused for Compound 1. The product obtained was a blue solid. ¹H NMR (400MHz, CDCl₃): δ 7.53 (s, 4H), 7.57 (t, J=5.5 Hz, 8H), 2.98 (q, J=7.5 Hz,4H), 2.88 (t, J=6.6 Hz, 8H), 2.04 (m, 8H), 1.40 (t, J=7.3 Hz, 6H).UV-vis spectrum: λ_(max)=622 nm (dichloromethane), Fluorometry:λ_(max)=757 nm (dichloromethane).

Intermediate B-9

Synthesis of Intermediate B-9 was performed according to the followingscheme:

Intermediate B-9 was prepared similarly to the procedure used forIntermediate B.

Intermediate E-9

Synthesis of Intermediate E-9 was performed according to the followingscheme:

Intermediate E-9 was prepared following the general method as was usedfor Intermediate E. ¹H NMR (400 MHz, CDCl₃): δ 7.39 (t, J=8.8 Hz, 8H),7.24 (d, J=9.2 Hz, 4H), 7.17 (t, J=7.3 Hz, 2H), 6.85 (d, J=9.2 Hz, 4H),4.54 (d, J=7.3 Hz, 2H), 3.57 (d, J=7.3 Hz, 4H), 2.51 (m, 1H), 2.09 (m,2H), 0.96 (d, J=6.6 Hz, 12H), 0.93 (d, J=6.6 Hz, 6H).

Compound 90

Synthesis of Compound 90 was performed according to the followingscheme:

Compound 90 was prepared from Intermediate E-9 following the sameprocedure used for Compound 1. ¹H NMR (400 MHz, CDCl₃): δ 8.05 (d, 8.8Hz, 4H), 7.32 (t, J=8.6 Hz, 4H), 7.24, (t, J=7.3 Hz, 4H), 7.09 (d, J=8.8Hz, 4H), 7.03 (t, J=7.5 Hz, 2H), 4.67 (d, J=7.3 Hz, 2H), 3.63 (d, J=7.3Hz, 4H), 2.99 (q, J=7.3 Hz, 4H), 2.67 (m, 1H), 2.16 (m, 2H), 1.39 (t,J=7.3 Hz, 6H), 1.01 (d, J=6.6 Hz, 12H), 1.04 (d, J=6.6 Hz, 6H). UV-visspectrum: λ_(max)=492 nm (dichloromethane), Fluorometry: λ_(max)=627 nm(dichloromethane).

Compound 91

Synthesis of Compound 91 was performed according to the followingscheme:

Compound 91 was prepared from Intermediate E-9 following the sameprocedure as for Compound 87. The product obtained was a blue solid. ¹HNMR (400 MHz, CDCl₃): δ 8.32 (d, 9.2 Hz, 4H), 7.35 (t, J=8.4 Hz, 4H),7.24, (d, J=9.2 Hz, 4H), 7.09 (d, J=9.2 Hz, 6H), 4.67 (d, J=7.3 Hz, 2H),3.63 (d, J=7.3 Hz, 4H), 2.67 (m, 1H), 2.16 (m, 2H), 1.39 (t, J=7.3 Hz,6H), 1.04 (d, J=6.6 Hz, 12H), 1.00 (d, J=6.6 Hz, 6H). UV-vis spectrum:λ_(max)=616 nm (dichloromethane), Fluorometry: λ_(max)=781 nm(dichloromethane).

Compound 92

Synthesis of Compound 92 was performed according to the followingscheme:

Compound 92 was prepared from Intermediate E-9 following the sameprocedure used for Compound 3. The product was isolated in a smallamount and characterized only by LCMS. UV-vis spectrum: λ_(max)=521 nm(dichloromethane), Fluorometry: λ_(max)=618 nm (dichloromethane).

Compound 93

Synthesis of Compound 93 was performed according to the followingprocedures:

Compound 93 was prepared from Intermediate E-9 following the sameprocedure used for Compound 1 with (DCM/acetic acid, room temperature, 1hour) but using phenanthrenequinone instead (1.1 eq). ¹H NMR (400 MHz,CDCl₃): δ 9.12 (, J=7.7 Hz, 2H), 8.47 (d, J=8.1 Hz, 2H), 8.22 (d, J=8.4Hz, 4H), 7.73 (t, J=7.4 Hz, 2H), 7.64 (t, J=7.7 Hz, 2H), 7.22-7.40 (m,12H), 7.09 (t, J=8.4 Hz, 2H), 4.76 (d, J=7.3 Hz, 2H), 3.72 (d, J=7.3 Hz,4H), 2.73 (m, 1H), 2.23 (m, 2H), 1.07 (d, J=6.6 Hz, 18H). UV-visspectrum: λ_(max)=604 nm (dichloromethane), Fluorometry: λ_(max)=745 nm(dichloromethane).

Compound 94

Synthesis of Compound 94 was performed according to the followingprocedures:

Compound 94 was prepared from Compound 25 following the same procedureas was used for Compound 70. ¹H NMR (400 MHz, CD₂Cl₂): δ 9.00 (d, J=8.0Hz, 2H), 8.47 (d, J=8.0 Hz, 2H), 8.03 (d, J=8.4 Hz, 4H), 7.77 (t, J=7.0Hz, 2H), 7.65 (t, J=7.7 Hz, 2H), 7.22-34 (m, 20H), 1.60-1.68 (m, 8H),1.32 (s, 24H), 1.23-1.32 (m, 8H), 1.12-1.16 (m, 8H), 0.85 (t, J=7.3 Hz,12H). UV-vis spectrum: λ_(max)=707 nm (dichloromethane), Fluorometry:λ_(max)=821 nm (dichloromethane).

Compound 95

Synthesis of Compound 95 was performed according to the followingprocedures:

Compound 95 is the same as Compound 69. Compound 95 was prepared fromIntermediate C by reaction with thionyl aniline in the presence oftrimethylsilyl chloride in dry pyridine at 80° C. for two hours. Thesame compound was also prepared by alkylation of Compound 4 withisobutyl tosylate as described for Compound 5.

Compound 96

Synthesis of Compound 96 was performed according to the followingprocedures:

Compound 96 was prepared from Compound 95 by reacting4-tert-butylbenzoyl chloride in the presence of zinc chloride inrefluxing DCM for 24 hours. Work-up with sodium bicarbonate, washing theorganic layer with water, drying, evaporation of the solvent and columnchromatography (DCM-2.5% ethyl acetate) produced pure product as a darkblue solid. ¹H NMR (400 MHz, CD₂Cl₂): δ 8.42 (d, J=8.8 Hz, 4H), 7.93 (d,J=8.8 Hz, 2H), 7.73 (d, J=8.8 Hz, 4H), 7.72 (d, J=8.4 Hz, 4H), 7.50 (d,J=8.4 Hz, 4H), 7.35-7.47 (m, 10H), 7.31 (d, J=7.7 Hz, 2H), 7.17-7.23 (m,6H), 4.71 (d, J=7.3 Hz, 2H), 2.67 (m, 1H), 1.31-1.38 (24H, 6Me&i-Bu).UV-vis spectrum: λ_(max)=587 nm (dichloromethane), Fluorometry:λ_(max)=725 nm (dichloromethane).

Compound 97 and 98

Synthesis of Compound 97 and Compound 98 were performed according to thefollowing procedures:

Compound 97 and Compound 98 were prepared following the same procedureused for Compound 70 using Compound 59 as the starting material.

¹H NMR for Compound 97 (400 MHz, CDCl₃): δ 8.88 (d, J=6.2 Hz, 2H), 8.48(d, J=6.2 Hz, 2H), 8.44 (d, J=8.8 Hz, 4H), 7.27 (d, J=8.8 Hz, 6H), 2.26(d, 8.8 Hz, 12H), 7.18 (d, J=8.8 Hz, 6H), 1.60 (m, 8H), 1.30 (s, 24H),1.23-1.31 (m, 8H), 1.06-1.14 (m, 8H) 0.87 (t, J=7.0 Hz, 12H). UV-visspectrum: λ_(max)=706 nm (dichloromethane), Fluorometry: λ_(max)=808 nm(dichloromethane).

Intermediate I

Synthesis of Intermediate I was performed according to the followingscheme:

Intermediate I was prepared as presented above. ¹H NMR (400 MHz, CDCl₃):δ 7.99 (d, J=8.8 Hz, 4H), 7.55 (s, 2H), 7.04 (d, J=8.8 Hz, 4H), 4.78 (t,J=7.0 Hz, 2H), 3.79 (d, J=6.6 Hz, 4H), 3.39 (t, J=7.0 Hz, 2H), 2.11-2.18(m, 4H), 1.85 (m, 2H), 1.50 (m, 2H), 1.04 (d, J=6.6 Hz, 12H).

Compound 99

Synthesis of Compound 99 was performed according to the followingscheme:

Compound 99 was obtained from Compound 2 and Intermediate I (1099-65)using standard alkylation conditions. ¹H NMR (400 MHz, CDCl₃): δ 7.97(m, 8H), 7.52 (s, 2H), 6.90-7.35 (m, 28H), 4.76 (m, 6H), 3.79 (d, J=6.6Hz, 2H), 3.75 (d, J=6.6 Hz, 4H), 2.67 (m, 1H), 2.05-2.25 (m, 6H), 1.52(m, 2H), 1.03 (m, 18H, 3 doublets overlapped).

Compound 100

Synthesis of Compound 100 was performed according to the followingprocedures:

Compound 100 was prepared using Intermediate B-7 by reaction withIntermediate D following the same procedure that was used for Compound2.

Compound 101

Synthesis of Compound 101 was performed according to the followingscheme:

Compound 101 was prepared as presented in the scheme above, using thesame conditions that were used for Compound 3. The reaction was easilymonitored by TLC. ¹H NMR (400 MHz, CDCl₃): δ 8.52 (d, J=8.8 Hz, 4H),7.96 (d, J=8.8 Hz, 4H), 7.52 (S, 2H), 4.85 (d, J=7.3 Hz, 2H), 4.77 (d,J=7.0 Hz, 2H), 4.66 (d, J=7.3 Hz), 3.80 (d, 6.6 Hz, 4H), 3.75 (d, J=6.2Hz, 4H), 1.68 (m, 1H), 2.05-2.25 (m, 8H), 1.51 (bs, 2H), 1.03 (3doublets overlapped).

Compound 102

Synthesis of Compound 102 was performed according to the followingscheme:

Compound 102 was prepared similarly to Compound 100 and Compound 101.Intermediate J was prepared by analogy to Intermediate I but using1,6-dibromohexane for alkylation of benzotriazole and later Stillecoupling with Intermediate B (instead of Suzuki coupling). ¹H NMR (400MHz, CDCl₃): δ 8.52 (d, J=8.8 Hz, 4H), 7.97 (d, J=8.8 Hz, 4H), 7.58 (s,2H), 7.25 (m, 8H), 7.16 (m, 12H), 7.09 (d, 8.8 Hz, 4H), 7.02 (t, J=7.3Hz, 4H), 4.84 (t, J=7.0, 2H), 4.78 (t, =7.3 Hz, 2H), 4.67 (d, J=7.3 Hz,2H), 3.80 (d, J=6.6 Hz, 4H), 2.67 (m, 1H), 2.13-2.23 (m, 6H), 1.52 (bs,4H), 1.04 (d, J=7.0 Hz, 18H).

Although the foregoing description has shown, described, and pointed outthe fundamental novel features of the present teachings, it will beunderstood that various omissions, substitutions, and changes in theform of the detail of the invention as illustrated, as well as the usesthereof, may be made by those skilled in the art, without departing fromthe scope of the present teachings. Consequently, the scope of thepresent teachings should not be limited to the foregoing discussion, butshould be defined by the appended claims. All patents, patentpublications and other documents referred to herein are herebyincorporated by reference in their entirety.

What is claimed is:
 1. A chromophore represented by formula (I):

wherein: L is independently C₁₋₈ alkyl or C₆₋₁₀ aryl; D₁ is selectedfrom the group consisting of: (1) C₆₋₁₀ aryl-NR′R″; and (2) C₆₋₁₀aryl-C₆₋₁₀ aryl-NR′R″; D₂ is selected from the group consisting of: (1)C₆₋₁₀ aryl-NR′R″; and (2) C₆₋₁₀ aryl-C₆₋₁₀ aryl-NR′R″; each R′ isindependently C₁₋₈ alkyl or C₆₋₁₀ aryl, wherein the C₆₋₁₀ aryl issubstituted by —C(═O)R; or each R′, together with the C₆₋₁₀ aryl towhich the nitrogen atom is attached to, forms a fused C₁₋₈ heterocyclicring comprising nitrogen; each R″ is independently C₁₋₈ alkyl or C₆₋₁₀aryl, wherein the C₆₋₁₀ aryl is optionally substituted by —C(═O)R; oreach R″, together with the C₆₋₁₀ aryl to which the nitrogen atom isattached to, forms a fused C₁₋₈ heterocyclic ring comprising nitrogen;or each R′ and R″, together with the C₆₋₁₀ aryl to which the nitrogenatom is attached to, forms a fused C₁₋₈ heterocyclic ring comprisingnitrogen; Het is selected from the group consisting of:

X is —S—; R_(a) is selected from the group consisting of: (1) hydrogen;(2) C₁₋₈ alkyl, optionally substituted by: (a) halo; (b) CN; (c) C₁₋₆alkoxy; (d) C₆₋₁₀ aryloxy, optionally substituted by halo, CN, or—C(═O)R; (e) C₃₋₁₀ cycloalkyl; or (f) C₆₋₁₀ aryl, optionally substitutedby halo or CN; (3) C₆₋₁₀ aryl, optionally substituted by: (a) halo; (b)CN; (c) C₁₋₈ alkyl; (d) C₁₋₆ alkoxy; or (e) C(═O)R; and (4) C₆₋₁₀heteroaryl, optionally substituted by: (a) halo; (b) CN; or (c) C₁₋₈alkyl; wherein the C₆₋₁₀ heteroaryl contains one or more nitrogenheteroatoms; R_(b) is selected from the group consisting of: (1)hydrogen; (2) C₁₋₈ alkyl, optionally substituted by: (a) halo; (b) CN;(c) C₁₋₆ alkoxy; (d) C₆₋₁₀ aryloxy, optionally substituted by halo, CN,or —C(═O)R; (e) C₃₋₁₀ cycloalkyl; or (f) C₆₋₁₀ aryl, optionallysubstituted by halo or CN; (3) C₆₋₁₀ aryl, optionally substituted by:(a) halo; (b) CN; (c) C₁₋₈ alkyl; (d) C₁₋₆ alkoxy; or (e) C(═O)R; and(4) C₆₋₁₀ heteroaryl, optionally substituted by: (a) halo; (b) CN; or(c) C₁₋₈ alkyl; wherein the C₆₋₁₀ heteroaryl contains one or morenitrogen heteroatoms; or R_(a) and R_(b), together with the carbon atomsto which they are attached, form a monocyclic ring or a polycyclic ringsystem selected from the group consisting of C₃₋₁₀ cycloalkyl and C₆₋₁₀aryl; wherein the monocyclic ring or polycyclic ring system isoptionally substituted by: (a) halo; (b) C₁₋₈ alkyl; (c) C₁₋₆ alkoxy; or(d) C₆₋₁₀ aryl, optionally substituted by C₁₋₆ alkoxy; each R isindependently C₁₋₈ alkyl, C₁₋₆ alkoxy, or C₆₋₁₀ aryl, wherein the C₆₋₁₀aryl is optionally substituted by C₁₋₈ alkyl; and i is 0; with theproviso that R_(a) and R_(b) are not both hydrogen.
 2. The chromophoreof claim 1, wherein: D₁ is selected from the group consisting of:

and D₂ is selected from the group consisting of:


3. The chromophore of claim 1, wherein: R_(a) is selected from the groupconsisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl, pentyl, hexyl, 2-ethylhexyl, 6-(3,5-difluorophenoxy)hexyl,2-butoxyethyl, 4-(4-cyanophenoxy)butyl, 5-(4-cyanophenoxy)pentyl,5-(4-acetylphenoxy)pentyl, cyclohexylmethyl, adamantylmethyl,2-cyclohexylethyl, benzyl, 4-fluorobenzyl, 2,6-difluorobenzyl, phenyl,4-(ethoxycarbonyl)phenyl, 3,4-dicyanophenyl, 4-pyridinyl, 2-pyrimidinyl,and 2-methylquinolin-4-yl; and R_(b) is selected from the groupconsisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl, pentyl, hexyl, 2-ethylhexyl, 6-(3,5-difluorophenoxy)hexyl,2-butoxyethyl, 4-(4-cyanophenoxy)butyl, 5-(4-cyanophenoxy)pentyl,5-(4-acetylphenoxy)pentyl, cyclohexylmethyl, adamantylmethyl,2-cyclohexylethyl, benzyl, 4-fluorobenzyl, 2,6-difluorobenzyl, phenyl,4-(ethoxycarbonyl)phenyl, 3,4-dicyanophenyl, 4-pyridinyl, 2-pyrimidinyl,and 2-methylquinolin-4-yl.
 4. The chromophore of claim 1, wherein: R_(a)and R_(b), together with the carbon atoms to which they are attached,form a monocyclic ring or polycyclic ring system selected from the groupconsisting of:


5. A wavelength conversion luminescent medium comprising an opticallytransparent polymer matrix and at least one luminescent dye comprising achromophore of claim
 1. 6. The wavelength conversion luminescent mediumof claim 5, wherein the optically transparent polymer matrix comprises asubstance selected from the group consisting of polyethyleneterephthalate, polymethyl methacrylate, polyvinyl butyral, ethylenevinyl acetate, ethylene tetrafluoroethylene, polyimide, amorphouspolycarbonate, polystyrene, siloxane sol-gel, polyurethane, andpolyacrylate, and combinations thereof.
 7. The wavelength conversionluminescent medium of claim 5, wherein the refractive index of theoptically transparent polymer matrix is in the range of 1.4 to 1.7. 8.The wavelength conversion luminescent medium of claim 5, wherein the atleast one luminescent dye is present in the optically transparentpolymer matrix in an amount in the range of 0.01 wt. % to 3 wt. %.
 9. Aphotovoltaic module comprising at least one photovoltaic device or solarcell and a wavelength conversion luminescent medium of claim
 5. 10. Thephotovoltaic module of claim 9, wherein the photovoltaic module furthercomprises a refractive, index matching liquid or optical adhesive %. 11.The photovoltaic module of claim 9, wherein the photovoltaic device orsolar cell comprises at least one device selected from the groupconsisting of a cadmium sulfide/cadmium telluride solar cell, a copperindium gallium diselenide solar cell, an amorphous silicon solar cell, amicrocrystalline silicon solar cell, and a crystalline silicon solarcell.
 12. The photovoltaic module of claim 9, wherein the wavelengthconversion luminescent medium is a film having a thickness in the rangeof 0.1 μm to 1 mm.
 13. A method for improving the performance of aphotovoltaic device of solar cell, wherein the method comprises: (a)applying the wavelength conversion luminescent medium of claim 5directly onto the light incident side of the photovoltaic device orsolar cell; or (b) encapsulating the wavelength conversion luminescentmedium of claim 5 in the photovoltaic device or solar cell.